JP2012096382A - Die for molding resin composite material, and method of manufacturing the resin composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a die used for forming a resin composite material by joining a base material to resin and capable of highly efficiently and promptly heating and cooling the base material, and a manufacturing method used for the resin composite material formed by joining the base material to the resin and capable of highly efficiently and promptly heating and cooling the base material.SOLUTION: The die for forming the resin composite material by arranging the base material in a cavity, then, introducing the resin to the cavity and joining the base material to the resin includes: a temperature sensor measuring the temperature of the base material; a heating source coming into contact with the base material and heating the base material; and a guiding passage introducing a cooling medium cooling the base material to an air gap between the heating source and the base material generated by separation of the heating source from the base material.

Description

  The present invention relates to a mold for forming a resin composite material in which a base material made of metal, glass, ceramic or the like and a resin are joined, and a resin in which the base material made of metal, glass, ceramic or the like and the resin are joined. The present invention relates to a method for manufacturing a composite material.

In many applications including electrical / electronic parts, electrical / electronic equipment, automotive parts, etc., there are parts that are lighter and more functional while ensuring predetermined performance such as electrical characteristics, strength, rigidity, and heat resistance. It has been demanded.
In order to meet such demands, conventionally, a composite material in which a part of a member made of metal, ceramics, glass or the like is made into a resin, and a member formed of resin are reinforced with a member made of metal, ceramics, glass, or the like. A resin composite material in which a highly rigid member (base material) made of metal, ceramics, glass, or the like and a resin is joined and integrated, such as a composite material, is used.

  As a method of joining the metal body and the resin body, after the surface of the metal body is subjected to a treatment such as forming irregularities, the metal body is inserted into the mold, and the resin is injected into the mold cavity. A method of injection molding is known (for example, Patent Documents 1 and 2). In this method, the resin in a molten (softened) state enters the irregularities on the surface of the metal body during the injection molding, and the resin remains in the irregularities even in the subsequent cooling process. A resin composite material in which the metal and the resin are firmly bonded can be formed while ensuring the adhesive strength.

  Regarding the bonding / integration of a substrate such as a metal and a resin by the anchor effect, the inventors of the present invention use a metal (including a metal having an anodized film formed on the surface), glass, ceramic, or paper and glass fiber as the substrate. By using a material obtained by laminating or plating a metal foil on a composite material such as a composite material of a material and a resin, the surface of the base is chemically treated to bond a polyfunctional reactive compound, and thereby the base It has been found that a chemical composite is produced between the (reactive compound) and the resin, and a resin composite material in which the base and the resin are firmly bonded can be obtained (for example, Patent Documents 3 and 4).

Not only these methods using the anchor effect, but many methods for firmly bonding a base such as metal, ceramics or glass and a resin, the base is heated to a predetermined temperature, and then the resin is brought into contact with the surface of the base. It is preferable to join.
Moreover, after making a base | substrate and resin contact (after holding for a predetermined time if necessary) so that it can transfer to production of the next resin composite material quickly, the obtained resin composite material can be taken out. It is preferable to cool to a predetermined temperature.

For this reason, heating and cooling the base | substrate arrange | positioned in the cavity of a metal mold | die is performed by heating and cooling a metal mold | die or a part of metal mold | die.
More specifically, a method of heating a mold body or a nest using an electric heater attached to a nest engraved with a cavity for inserting the mold body or a base material is known.
There are also known a method of heating a mold by flowing a heat medium such as steam or hot water through a flow path formed in the mold, and a method of heating a mold using electromagnetic induction.
On the other hand, in the case of cooling at least a part of a mold, a method of cooling through a cooling medium such as cold water through a flow path formed in the mold is known. Also known is a method of cooling the mold from the outside using cold air.

International Publication No. WO2004 / 041532 JP 2007-203585 A JP 2009-114504 A International Publication No. WO2009 / 157445

  However, since the mold has a certain size and mass, heating or cooling the substrate by heating or cooling at least a part of the mold requires a large amount of heat to heat the mold. It is necessary to supply. Similarly, a large amount of heat needs to be taken from the mold to cool the mold.

  For this reason, there existed a problem that the cost of heating and cooling of a base material became high, and the problem that production efficiency fell because much time was required for the heating and cooling of a base material.

  Therefore, the present invention provides a mold for joining a base material and a resin to form a resin composite, and capable of heating and cooling the base material with high efficiency and speed, Another object of the present invention is to provide a method for producing a resin composite material in which a base material and a resin are joined, wherein the base material can be heated and cooled quickly and efficiently.

  Aspect 1 of the present invention is a mold for forming a resin composite by joining a base material and the resin by introducing a resin into the cavity after placing the base material in the cavity. A temperature sensor for measuring the temperature of the base material; a heating source for heating the base material in contact with the base material; and the heating source and the base generated when the heating source is separated from the base material. A metal mold including a guide path for introducing a cooling medium for cooling the base material in a gap between the base material and the material.

  A second aspect of the present invention is the mold according to the first aspect, wherein the heating source is in contact with and separated from a surface of the substrate opposite to a surface to be bonded to the resin.

  According to the third aspect of the present invention, a step of placing a base material in a cavity of a mold, a heating source is brought into contact with the base material, the base material is heated to a predetermined temperature, and then a resin is introduced into the cavity. And a step of cooling the substrate by introducing a cooling medium into a gap between the substrate and the heat source generated by separating the heating source from the substrate. It is a manufacturing method.

  Aspect 4 of the present invention is the manufacturing method according to aspect 3, wherein the heating source is in contact with a surface of the substrate opposite to the surface in contact with the resin.

  In aspect 5 of the present invention, the base material is formed of a hydroxide, a hydrated oxide, an ammonium salt, an amine compound, a carboxylate, a phosphate, a carbonate, a sulfate, a silicate, and a fluoride. Or a reactive compound layer comprising a water silanol-containing triazine thiol derivative disposed on the metal removal compound film and at least one selected from the group consisting of: 4. The production method according to 4.

  Aspect 6 of the present invention is the manufacturing method according to aspect 5, wherein the metal compound film contains at least one of a metal hydrated oxide and a hydroxide.

  Aspect 7 of the present invention is characterized in that the metal compound film includes at least one phosphate selected from the group consisting of a metal hydrogen phosphate, a metal dihydrogen phosphate, and a metal phosphate. It is a manufacturing method of aspect 5.

  Aspect 8 of the present invention is characterized in that the resin is a thermoplastic resin, and the predetermined temperature is in the range of −50 ° C. to + 100 ° C. from the glass transition point or melting point of the thermoplastic resin. 7. The production method according to any one of 7 above.

  Aspect 9 of the present invention is any one of the aspects 3 to 7, wherein the resin is a thermosetting resin, and the predetermined temperature is in the range of + 0 ° C. to + 100 ° C. from the curing temperature of the thermosetting resin. It is a manufacturing method of crab.

  By using the mold and the method for producing a resin composite member of the present invention, it is possible to heat and cool the base material for the resin composite material in which the base material and the resin are joined with high efficiency and speed.

FIG. 1 is a cross-sectional view of a mold 100 according to the present invention, showing a state in which a substrate 200 can be heated. FIG. 2 is a cross-sectional view of the mold 100 according to the present invention, showing a state in which the substrate 200 can be cooled. FIG. 3 shows (a) time change of the position of the heating core, (b) time change of the temperature of the substrate, (c) time change of on / off of the cooling medium supply device, and (d) opening and closing of the mold. It is a graph which shows a time change typically. FIG. 4 is a cross-sectional view schematically showing a part of a preferred substrate 200 according to the present invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the following description, terms indicating a specific direction and position (for example, “up”, “down”, “right”, “left” and other terms including those terms) are used as necessary. These terms are used for easy understanding of the invention with reference to the drawings, and the technical scope of the present invention is not limited by the meaning of these terms.

1. Mold FIG. 1 is a sectional view of a mold 100 according to the present invention. The state which can heat the base material 200 is shown. Although details will be described later, the substrate 200 can be heated by contacting the substrate 200 with a heating core 300 that functions as a heating source and is movable in the vertical direction in the figure.
Compared with the case where the conventional mold is heated and the base material is heated by thermoelectric conduction from the heated mold, the base material 200 can be directly heated, so that the base material 200 can be heated efficiently and quickly. Is possible.

  FIG. 2 is a cross-sectional view of the mold 100 according to the present invention, showing a state in which the substrate 200 can be cooled. As will be described in detail later, the heating core 300 is separated from the base material 200 and moves downward from the cooling medium inlet 22a. For this reason, a gap 26 is formed between the substrate 200 and the heating core 300. For example, a cooling medium such as air passes through the cooling medium guide path 22 and is introduced into the gap 26 from the cooling medium introduction port 22a. The base material 200 can be cooled by the cooling medium coming into contact with the base material 200.

  Compared to the case where the conventional mold is cooled and the base material is cooled by thermoelectric conduction to the cooled mold, the base material 200 can be directly cooled, so that the base material 200 can be cooled efficiently and quickly. Is possible.

Details of the mold 100 will be described below.
The mold 100 includes a fixed mold (upper mold) 15 and a movable mold (lower mold) 11.
The fixed-side mold 15 and the movable-side mold 11 are fixed, for example, by using a vacuum suction device as a mold opening / closing device so that the fixed-side mold 15 and the movable-side mold 11 are in contact (closed state). A state in which the side mold 15 and the movable side mold 11 are separated (open state) can be obtained. 1 and 2 both show a closed state.

The arrangement of the molds is not limited to the form shown in FIGS. 1 and 2, and the upper mold 15 may be a movable mold, the lower mold 11 may be a fixed mold, Both lower molds 11 may be movable molds.
Furthermore, the invention according to the present invention is not limited to the upper and lower molds such as the upper mold and the lower mold, and the base 200 can be inserted into the cavity. Any type of mold may be used as long as it is a mold capable of taking out the resin composite material obtained by bonding.

  The upper mold 15 is provided with an upper mold cavity 16. A gate 18 and a runner 19 are provided on the upper part of the upper mold cavity 16. Then, a molten resin 24 supplied from a nozzle of a molten resin supply device such as an injection mechanism of an injection molding machine (not shown) is supplied to the upper mold cavity 16 through the runner 19 and the gate 18, and is cooled and solidified. .

The lower mold 11 is provided with a lower mold cavity 12 in which the substrate 200 can be disposed.
When the mold 100 is closed, the lower mold cavity 12 and the upper mold cavity 16 are connected to form one cavity.
In addition, the lower mold cavity 12 and / or the upper mold cavity 16 may be installed in the core and provided in the core. The use of the core has an advantage that the shape of the cavity can be easily changed simply by replacing the core.

In addition, a heating core 300 that functions as a heating source that contacts the substrate 200 and heats the substrate 200 is disposed below the lower mold cavity 12. The heating core 300 is movable in the vertical direction in FIGS. 1 and 2.
In the state shown in FIG. 1, the heating core 300 is positioned above and is in contact with the substrate 200, and can heat the substrate 200.

On the other hand, in the state shown in FIG. 2, the heating core 300 is separated from the base material 200 and is located below the cooling medium inlet 22a. When the heating core 300 is separated from the base material 200, a gap 26 is formed between the base material 200 and the heating core 300.
A cooling medium can be introduced into the gap 26 via the cooling medium guide path 22 and the cooling medium introduction port 22a disposed inside the lower mold 11. The material 200 is cooled.

The heating core 300 is made of a material such as a metal, for example, and includes a temperature sensor 14 for measuring the temperature (surface temperature) of the substrate 200 and a heater 17 for heating the heating core.
The material used for the heating core is preferably a material having excellent thermal conductivity so that heat from the heater 17 can be uniformly distributed. Examples of such materials include beryllium copper and steel.

  The heating core 300 can preferably be in contact with an area of 50% or more of the area where the resin 24 of the substrate 200 is bonded so that the substrate 200 can be heated more uniformly. Moreover, the heating core 300 is. In order to suppress excessive heating of the substrate 200, it is possible to contact with an area of 120% or less of the area where the resin 24 of the substrate 200 is bonded. The contact between the heating core 300 having such a preferred area and the base material 200 is, for example, immediately below the portion where the base material 200 and the resin 24 are joined, and on the opposite side of the surface of the base material 200 where the resin 24 is joined. It is preferable that the surface is in the vicinity of the joint between the substrate 200 and the resin 24.

In the embodiment shown in FIG. 1, the heating core 300 is in contact with the surface on the opposite side of the surface of the substrate 200 that is in contact with the resin 24.
In such an embodiment, the heating core does not interfere with the resin 24. In addition, since the distance in the thickness direction of the substrate is generally shorter than the distance in the width direction, there is an advantage that the surface of the substrate 200 in contact with the resin can be heated quickly.

  However, the present invention is not limited to the embodiment shown in FIG. 1. For example, the heating core 300 may be disposed so as to be in contact with or separated from the side surface of the base material 200. The heating core 300 may be arranged so as to be in contact with or separated from the same surface as the surface in contact (for example, a portion not in contact with the resin 24).

The temperature sensor 14 may be either a contact type or a non-contact type. Examples of the contact type temperature sensor include a thermocouple, a resistance temperature detector, and a thermistor temperature sensor. When using a contact-type temperature sensor, when the heating core 300 is contacting the base material 200, the temperature sensor 14 must also be arrange | positioned so that the base material 200 may be contacted.
An example of the non-contact temperature sensor is an infrared sensor. When the temperature sensor 14 is a non-contact type, the temperature of the base material 200 can be measured even if the temperature sensor 14 is not in contact with the base material 200, so that the heating core 300 is not in contact with the base material 200. There is an advantage that the temperature of the substrate 200 can be measured.

  As shown in FIGS. 1 and 2, the side surface of the temperature sensor 14 is preferably surrounded by a sensor core 13. The sensor core 13 has an effect of suppressing heat from the heater 17 being transmitted to the temperature sensor 14 and affecting the temperature measurement result of the temperature sensor 14. That is, by providing the sensor core 13, the temperature sensor 14 can measure the temperature of the substrate 200 more accurately. The sensor core 13 is preferably made of a material having low thermal conductivity, and for example, ceramic, titanium, and stainless steel can be used as such a material.

  In the embodiment shown in FIG. 1, the temperature sensor 14 is arranged inside the heating core 300 as described above. However, the temperature sensor 14 is not limited to such an embodiment. A temperature sensor or a non-contact sensor may be disposed outside the heating core 300 (for example, inside the upper mold 15).

A plurality of heating cores 300 and temperature sensors 14 may be arranged in the mold 100 according to the arrangement of the upper mold cavity 16 into which the resin 24 bonded to the base material 200 is introduced.
If necessary, a plurality of temperature sensors 14 may be arranged inside and / or outside the heating core 300. A plurality of temperature measurement values obtained by using a plurality of temperature sensors 14 are taken into a data processing device, for example, and the temperature of the substrate 200 is calculated using numerical values such as an average value, a median value, a maximum value, and a minimum value. It becomes possible to determine by.

As the heater 17, any known heating body (heater) capable of heating and heating the heating core 300 may be used. Examples of such a heater include a resistance heating type heater, an induction heating type heater, and a heating medium (heating body) such as hot water or steam flowing through a flow path provided in the heating core 300. In the example shown in FIG. 1, the heater 17 is a resistance heating type heater disposed in a hole drilled.
The heater 17 has a calorific value sufficient to raise the temperature of the substrate 200 to a predetermined temperature. Preferably, the heater 17 can heat the substrate 200 to 400 ° C. or higher.

  In the embodiment shown in FIG. 1, the heater 17 is arranged inside the heating core 300, but instead of or in addition to this, for example, the heater 17 is arranged in contact with the lower part of the heating core 300. Can be arranged outside the heating core 300.

The heating core 300 is preferably arranged so as to have a gap 20 between the side surface and the lower mold 11. This is because, by having the gap 20, it is possible to suppress the amount of heat of the heating core 300 from being taken away by the lower mold 11 due to heat transfer.
The gap 20 is preferably 0.5 mm or more. This is because the above-described effect can be obtained more reliably.
Note that having the gap 20 between the side surface of the heating core and the lower mold 11 is not only a state where the entire side surface of the heating core 300 is not completely in contact with the lower mold 11, but also one of the side surfaces of the heating core 300. Needless to say, this includes a state where the part is in contact with the lower mold 11.

  The cross-sectional shape of the heating core 300 (the shape in a plane perpendicular to the direction in which the heating core 300 moves up and down) may be any shape, but the preferred cross-sectional shape is a circle. This is because if the cross-sectional shape is circular, there is no anisotropy of thermal expansion, and handling is easy.

The lower mold 11 functions as a cooling medium guiding path 22 through which a gas or liquid functioning as a cooling medium can pass and an outlet of the cooling medium guiding path 22 (an outlet facing the air gap 26 or the heating core 300). And a cooling medium inlet 22a.
The cooling medium guiding path 22 and the cooling medium introduction port 22a can be installed, for example, by making a hole in the lower mold 11 with a drill.

2. Manufacturing Method Next, a method for manufacturing a resin composite using the above-described mold 100 will be described in detail below.

  First, after the base material 200 is disposed in the lower mold cavity 12 of the lower mold 11 with the upper mold 15 and the lower mold 11 opened (separated), the upper mold 15 and the lower mold 11 are closed (shown in FIG. 1). Contact).

Hereinafter, description will be made with reference to FIG.
FIG. 3 shows (a) time variation of the position of the heating core, (b) time variation of the temperature of the substrate, and (c) time variation of on / off of the cooling medium supply device (that is, whether or not the cooling medium is supplied). And (d) is a graph schematically showing a time change of opening and closing of the mold. In any graph, the horizontal axis indicates the passage of time, and the horizontal axis (the passage of time) of all the graphs is the same (that is, the same time has elapsed if the position on the horizontal axis is the same).

In the initial state, as described above and as shown in FIG. 3D, the mold is in a closed state, and the heating core 300 is positioned at the lowest position. Here, the “lowest level” means the lowest position when the heating core 300 moves up and down. When the heating core 300 is at the lowest level, for example, as shown in FIG. It is located at a position (lower side) lower than the path 22a.
In the initial state, the cooling medium supply device does not operate as shown in FIG. 3C, and therefore the cooling medium is not supplied to the gap 26.
Further, in the initial state, the substrate 200 has an initial temperature such as room temperature.

When the heating core 300 reaches a predetermined temperature by the heater 17 of the heating core 300, the heating core 300 is raised from the lowest level to the highest level as shown in FIG. Here, the “highest position” means the uppermost position (the highest position) when the heating core 300 moves up and down. When the heating core 300 is located at the highest position, the heating core 300 contacts the substrate 200 as illustrated in FIG.
The heating core 300 may be raised (and lowered) by connecting the heating core 300 to a device such as an air cylinder that can be driven (raised and lowered) and stopped by a signal.

  And the temperature of the base material 200 rises as shown in FIG.3 (b). The increase in the substrate temperature is monitored by the temperature sensor 14, and the heat generation amount of the heater 17 may be feedback controlled as necessary using the measurement result by the temperature sensor 14.

  When the temperature of the substrate 200 reaches the target temperature, the resin 24 (molten resin) is introduced into the upper mold cavity 16 of the upper mold 15. When the introduced resin 24 reaches the surface of the substrate 200, the resin 24 starts to join the substrate 200.

For example, the resin 24 is introduced into the upper mold cavity 16 after the nozzle of the injection mechanism of the injection molding machine is connected to the runner 19, and then the resin 24 is transferred from the injection mechanism to the upper mold cavity 16 through the runner 19 and the gate 18. You may carry out by injecting.
The injection of the resin 24, for example, confirms the bonding strength and its variation in addition to the molding appearance, the temperature of the barrel and nozzle for dissolving the resin 24, the injection speed, the holding pressure for pressing the resin 24 against the substrate 200, It is preferable to carry out by controlling conditions such as pressure holding time.

  The target temperature of the substrate 200 varies depending on the type of the substrate 200 and the type of the resin 24, but is, for example, 140 ° C to 550 ° C. When the resin 24 is a thermoplastic resin, the target temperature of the substrate 200 is preferably in the range of −50 ° C. to + 200 ° C. of the glass transition point or melting point of the resin 24, more preferably −30 ° C. to 150 ° C. When the resin 24 is a thermosetting resin, it is preferably in the range of + 0 ° C. to 100 ° C. of the curing temperature of the resin 24, and more preferably in the range of + 0 ° C. to 80 ° C.

When the resin 24 is a thermoplastic resin, the base material 200 is heated by the molten resin 24, the temperature of the surface of the base material 200 rises, and the temperature at which the resin 24 flows and is joined by a chemical reaction is maintained. Preferably has a glass transition point or a melting point of −50 ° C. or higher (over 50 ° C. lower than the melting point). If the temperature exceeds + 200 ° C., the resin 24 decomposes and the physical properties are increased. This is because it may decrease.
On the other hand, when the resin 24 is a thermosetting resin, in order for the resin 24 to flow on the surface of the substrate 200 and join by a chemical reaction, the temperature is preferably equal to or higher than the curing temperature. This is because if the temperature exceeds 100 ° C. higher than the curing temperature, the curing rate is too high and bonding by chemical reaction may be insufficient.

  In an even more preferred embodiment in which the resin 24 is a thermoplastic resin, when the resin 24 has both a glass transition point and a melting point, the melting point ranges from −50 ° C. to + 200 ° C. (more preferably, the melting point When the resin 24 does not have a melting point and has only a glass transition point, the range of −50 ° C. to + 200 ° C. of the glass transition point (more preferably, the glass transition point). −30 ° C. to 150 ° C.).

  In the example shown in FIG. 3B, the temperature of the substrate 200 is maintained at the target temperature after reaching the target temperature, but fluctuates within a predetermined temperature range, for example, within a predetermined range equal to or higher than the target temperature. May be.

When the base material 200 is maintained at the target temperature (or within a predetermined temperature range) and the resin 24 and the base material are sufficiently joined, and the introduction of the resin 24 into the upper mold cavity 16 is completed, FIG. As shown, the heating core 300 starts to descend from the highest level to the lowest level.
By this lowering, the heating core 300 is separated from the base material 200, and a gap 26 is generated between the base material 200 and the heating core 300.
When the heating core 300 reaches below the cooling medium introduction port 22a, the cooling medium supply device is turned on and the cooling medium is introduced into the gap 26 as shown in FIG. The cooling medium introduced into the gap 26 cools the substrate 200. In addition, the resin 24 can be cooled by cooling the base material 200.

As a cooling medium supply device, for example, a refrigeration air generator may be connected to the cooling medium guiding path 22.
As the cooling medium, it is preferable to use air because it is inexpensive and easy to handle, but in addition to this, a gas such as nitrogen, carbon dioxide or a mixed gas thereof, or a liquid such as water or brine is used. You can also. However, when using a liquid, it is preferable to consider the waterproofing of the temperature sensor 17 and the hole into which the sensor is inserted.

  The substrate 200 is cooled to a predetermined temperature at which the obtained resin composite material can be taken out from the mold 100 (to the same temperature as the initial temperature in the example of FIG. 3B). When this predetermined temperature is reached, the mold 100 is opened as shown in FIG. The resin composite material thus obtained can be taken out.

3. Base Material The base material 200 will be described below.
The material that can be used as the substrate 200 is not particularly limited. For example, a metal, glass, ceramic, or a composite material in which a metal foil is laminated or plated on the surface (for example, a composite of paper, glass fiber material, and resin). Material). A material in which a new layer is formed by surface treatment, such as a metal on which an anodized film is formed, may be used as the substrate 200.

FIG. 4 is a cross-sectional view showing a particularly preferred substrate 200.
A substrate 200 shown in FIG. 4 has a metal compound film 2 on the base material 1 and further has a reactive compound layer 3 on the metal compound coating.
Here, the base material 1 is a composite material (for example, a composite material of paper, a glass fiber material, and a resin) in which metal foil is laminated or plated on a metal, glass, ceramic, or a surface. The base material 1 may be a metal on which an anodized film is formed.

  Although details will be described later, the metal compound film 2 is a group consisting of hydroxide, hydrated oxide, ammonium salt, amine compound, carboxylate, phosphate, carbonate, sulfate, silicate, and fluoride. It is a film containing at least one selected from.

  The reactive compound layer 3 is a molecular layer including at least one selected from the group consisting of alkoxysilane-containing triazine thiol derivatives, silanol-containing triazine thiol derivatives, and dehydrated silanol-containing triazine thiol derivatives.

  The inventor of the present application uses the base material 200 having the metal compound film 2 on the base material 1 and further having the reactive compound layer 3 on the metal compound coating, so It has been found that a resin composite material can be obtained that is extremely strongly bonded.

Although details will be described later, the alkoxysilane-containing triazine thiol derivative or the like contained in the reactive compound layer 3 disposed (coated) on the metal compound film 2 is changed as follows. It is considered that the resin 24 is strongly bonded.
However, this mechanism is expected from the obtained results, and does not limit the scope of the present invention.

The alkoxysilane-containing triazine thiol derivative contained in the reactive compound layer 3 applied to the metal compound film 2 is first converted into a silanol-containing triazine thiol derivative by hydrolysis. As a result, a hydrogen bond-like loose bond is generated between the metal compound film 2 and the metal compound film 2.
Next, by heating the substrate 200 to a predetermined temperature, the hydroxide, hydrated oxide, ammonium salt, amine compound, carboxylate, phosphorus contained in the silanol part of the silanol-containing triazine thiol derivative and the metal compound film 2 A dehydration or dehalogenation bond reaction occurs with at least one of an acid salt, carbonate, sulfate, silicic acid, fluoride, and the like, and the silanol-containing triazine thiol derivative is changed to a dehydrated silanol-containing triazine thiol derivative. As a result, the reactive compound is chemically bonded to the metal compound film.
When the resin 24 is a thermoplastic resin, the resin molecules in a heated and molten state are in contact with the reactive compound layer 3, and when the resin 24 is a thermosetting resin, the resin molecules in a fluid state are in contact with the reactive compound layer 3. Thus, a chemical bond is formed between the triazine thiol derivative part of the dehydrated silanol-containing triazine thiol derivative (triazine thiol metal salt part or triazine thiol derivative bound with bismaleimides).

  In one of the preferred embodiments of the present invention, the temperature of the substrate 200 (surface temperature) when the substrate 200 having the reactive compound layer 3 on the surface is brought into contact with the fluidized resin 24 in the mold 100. Is measured by the temperature sensor 14, and the resin 24 is injected into the upper mold cavity 16 in a state heated to an appropriate temperature, whereby the resin and the substrate are firmly bonded.

  The terms “reactive compound” and “reactive compound layer” used in the present specification are at least one selected from the group consisting of alkoxysilane-containing triazine thiol derivatives, silanol-containing triazine thiol derivatives, and dehydrated silanol-containing triazine thiol derivatives. Means a molecular layer comprising one.

  Details of the substrate 200 according to the preferred embodiment shown in FIG. 4 (hereinafter may be referred to as “preferable substrate 200”) will be described below.

In order to obtain a resin composite material using the preferred substrate 200, it is necessary to carry out the following steps (treatments).
1). Metal compound treatment to form metal compound film 2 on the surface of base material 1 2). Reactive compound treatment 3 in which a reactive compound containing an alkoxysilane-containing triazine thiol derivative is applied on the metal compound film 2 to form a reactive compound layer 3 containing a dehydrated silanol-containing triazine thiol derivative on the metal compound film 2 ). Joining step of joining the resin 24 by heating the base member 200 to a predetermined temperature using the preferable base member 200 and the mold 100 obtained by the reactive compound treatment. In the manufacturing method shown in “2. Manufacturing method”, this can be realized by using a preferable substrate 200.
Therefore, the metal compound treatment and the reactive compound treatment will be described below.

I. Metal compound treatment Metal compound film (also referred to as “compound film”) is a hydroxide, hydrated oxide, ammonium salt, amine compound, carboxylate, phosphate, carbonate, sulfate, silicate, And a film containing at least one selected from the group consisting of fluorides.
Preferably, the total of these hydroxides, hydrated oxides, ammonium salts, amine compounds, carboxylates, phosphates, carbonates, sulfates, silicates, and fluorides is the main component of the metal compound film (For example, 50% or more of the metal compound film 2 by mass ratio).

  Details of the metal compound treatment are shown below.

I-1. Base material Base material 1 is formed by laminating or plating a metal foil on various metals, metal having a film formed on the surface, glass, ceramics, and a composite material such as a composite substrate of paper and / or glass fiber material and resin. It is possible to use materials and the like.
Preferred metals used for the base material 1 include iron and alloys thereof, steel (including alloy steel), stainless steel, aluminum and alloys thereof, copper and alloys thereof, magnesium and alloys thereof, titanium and alloys thereof, these metals and alloys. The plated product can be exemplified.
As the ceramic, an amorphous or crystalline metal oxide can be used. Examples of preferred amorphous metal oxides are borosilicate glass, soda glass, quartz glass, and lead glass. Examples of crystalline metal oxides include alumina, β-alumina, zirconia, silica, magnesia, beryllia, zinc oxide, titania, murania, tin oxide, ITO, ferrite, zircon, aluminum titanate, barium titanate, etc. It is done. In addition, the metal with a film formed on the surface formed an aluminum alloy formed with alumina called anodized, a magnesium alloy formed with magnesia, and titania as a metal material formed with the crystalline metal oxide film by anodizing treatment. Examples thereof include titanium and a titanium alloy, zinc and a zinc alloy formed with zinc oxide, and a tin and tin alloy formed with tin oxide.
As a material obtained by laminating a metal foil on a base material in which a resin is reinforced with paper or glass fiber material, or by plating a metal and an alloy, there are various substrate materials.
The base material 1 made of these suitable metals is easy to form the metal compound film 2. That is, as shown in the potential-pH diagram, these suitable metals have a wide pH range that reacts with acids and alkalis, and it is relatively easy to form a metal compound film. Furthermore, there is an advantage that the obtained metal compound film 2 has excellent stability.

For the formation of the base material 1, various methods such as extrusion, rolling, pressing, forging, casting, die casting, and sintering can be used. Moreover, you may adjust a shape, a dimension, etc. by adding machining to the molding material obtained after shaping | molding by these methods.
The shape of the base material 1 may be any shape including a plate (sheet) shape, a tubular shape, a cylindrical shape, a rectangular parallelepiped shape, a conical shape, and a pyramid shape.

I-2. Cleaning treatment The surface of the base material 1 becomes non-uniform due to segregation and oxide film produced in the manufacturing process, or the rolling oil, cutting oil, press oil, etc. used during processing and molding adhere to it, or rusting occurs during transportation. It may get dirty due to fingerprints. For this reason, depending on the state of the surface of the base material 1, it is preferable to perform a cleaning process using an appropriate cleaning method. However, cleaning is not an essential process.

  Cleaning methods include physical methods such as grinding, buffing, and shot blasting, for example, electrochemical methods in which electrolytic treatment is performed in an alkaline degreasing liquid and cleaning is performed using generated hydrogen and oxygen, alkaline and acidic methods. Further, a chemical method using a neutral solvent (cleaning agent) can be used.

  It is preferable to use a chemical cleaning method from the viewpoint of simplicity of operation and cost advantage. Cleaning agents used for chemical cleaning include acidic cleaning agents such as sulfuric acid-fluorine, sulfuric acid-phosphoric acid, sulfuric acid, sulfuric acid-oxalic acid, and nitric acid, sodium hydroxide, sodium carbonate, and sodium bicarbonate. Any industrially usable cleaning agent may be used, including alkaline cleaners, such as alkaline, boric acid-phosphoric acid, sodium phosphate, condensed phosphoric acid, fluoride, silicate. . Since it is inexpensive, has good operability, and does not roughen the surface of the base material 1, a weak alkaline aqueous solution (weak alkaline detergent) such as condensed phosphoric acid, sodium phosphate, or sodium bicarbonate is used. Is preferred.

  After performing the cleaning treatment, it is indispensable to form a desired metal compound film 2 on the surface of the base material 1 by performing a surface roughening treatment as necessary, and then performing a metal compound treatment described later. Therefore, in the cleaning process that is the previous process, the deposits on the surface of the base material 1 are removed, and the metal oxide film is removed and homogenized to the extent that the process in the next process is not hindered. It is preferable that the material 1 is not excessively damaged by dissolution or the like during cleaning. For this reason, when the base material 1 is made of iron, a stainless steel material, an aluminum alloy material, or a titanium material, a weak etching type such as sodium orthosilicate, sodium metasilicate, or sodium phosphate in which the base material 1 is slightly dissolved is used. It is preferable to use a non-etching type that does not dissolve the surface.

  As the non-etching type cleaning agent, it is preferable to use a cleaning agent mainly composed of condensed phosphate. As the condensed phosphate, sodium pyrophosphate, sodium tripolyphosphate, sodium tetrapolyphosphate, and the like can be used. For example, the alkali component is 30 g / L (of which the condensed phosphate accounts for 50-60%). An aqueous solution having a pH of about 9.5 can be used. A good cleaning can be performed at a treatment temperature of 40 to 90 ° C. and a treatment time of about 5 to 20 minutes. After washing, wash with water. The preferred concentration of the alkali component is 20 to 100 g / L, more preferably 20 to 60 g / L, most preferably 20 to 40 g / L, the preferred pH is 9 to 12, and the preferred temperature is 40 ° C. to 60 ° C. By immersing the base material 1 in a weak alkaline aqueous solution that satisfies such conditions, the surface can be cleaned and made uniform.

  In addition to the above, borax, sodium orthosilicates of Group I and II, sodium silicate, sodium carbonate, sodium bicarbonate, sodium salts such as borax, primary sodium phosphate, secondary sodium phosphate, Various sodium phosphates such as sodium triphosphate and phosphates such as sodium hexametaphosphate may be used.

  When copper or a copper alloy is used for the base material 1, the above weak etching type or weak acid can be used. For example, it can be washed at a temperature of 30 to 50 ° C. with a solution of less than 1% of a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid and a mixed solution thereof.

  On the other hand, when magnesium or a magnesium alloy that hardly reacts with alkali is used as the base material 1, an alkali such as sodium hydroxide or potassium hydroxide can be used in addition to the above-described cleaning agent. Preferable degreasing conditions use, for example, a sodium hydroxide aqueous solution having a concentration of 10 to 100 g / L and a temperature of 50 to 90 ° C.

1-2. Metal Compound Treatment After performing the above-described cleaning treatment and / or roughening treatment as necessary, the surface of the base material 1 is subjected to a metal compound treatment (also referred to as “compound treatment”) to obtain a hydroxide, A metal compound film 2 containing at least one of hydrated oxide, ammonium salt, carboxylate, phosphate, carbonate, sulfate, silicate and fluoride is formed.
The metal compound treatment is performed by immersing in, for example, an aqueous solution of at least one of the following compounds and acids.

  The “metal” in the “metal compound coating” shown in this specification refers to the metal contained in the base material 1 and the metal contained in the solution (metal compound treatment liquid) used for the metal compound treatment described below in detail. Means at least one of

  The metal compound treatment can be roughly divided into an alkali treatment using an alkaline solution and an acid treatment using an acidic solution. Details of each are shown below.

  The alkali treatment is performed by using a solution showing neutrality or alkalinity described in detail below, for example, by immersing in these solutions. In the alkali treatment, it is preferable to use an aqueous solution of a compound exhibiting neutral to weak alkalinity at pH 7-12.

With the acid treatment, a metal compound treatment is performed by immersing in a solution having the acidity described below in detail, for example. In the acid treatment, it is preferable to use an aqueous solution of a compound exhibiting weak acidity of pH 2 to 5.
The alkali treatment and the acid treatment will be described with reference to the solutions specifically used below.

I-2-1. Alkali treatment The metal compound treatment can be performed by immersing the base material 1 in a metal compound treatment solution (an aqueous solution of an alkali compound) used for the alkali treatment.

(1) Group I element hydroxides, Group I element salts, Group II element hydroxides, Group II element salts Group I elements such as lithium, sodium, potassium, rubidium or cesium (I in the periodic table) Group I element hydroxides; Group I element salts; Beryllium, magnesium, calcium, strontium or barium group II elements (group II elements in the periodic table) and group II element salts An aqueous solution of can be used. By using any of these, the metal compound film 2 mainly composed of hydroxide is generated on the surface of the base material 1. An example of a hydroxide that is a main component of such a metal compound film 2 is a metal hydroxide (wherein the metal is a metal contained in the base material 1). Further, as the metal compound film 2, a metal hydrated oxide is generated instead of or together with the metal hydroxide.

The group I element hydroxide, group I element salt, group II element hydroxide and group II element salt used in the metal compound treatment are shown in more detail.
Examples of group I element hydroxides include sodium hydroxide and potassium hydroxide. For example, when the metal compound treatment is performed using an aqueous solution of sodium hydroxide, the treatment is preferably performed at a sodium hydroxide concentration of 0.04 to 100 g / L and a temperature of 30 to 80 ° C. Thereby, a metal compound film 2 mainly composed of metal hydroxide and / or metal hydrated oxide is formed on the surface of the metal substrate 1.

  The salt of a group I element is a salt generated by a group I element and an acid, and an aqueous solution of the salt is a metal salt exhibiting alkalinity. It is a salt produced mainly by combining a weak acid and a group I element. Examples of such a group I element salt include sodium orthosilicate, sodium metasilicate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, Examples include sodium acetate, potassium acetate, sodium laurate, potassium laurate, sodium palmitate, potassium palmitate, sodium stearate, and potassium stearate. For example, when the metal compound treatment is performed using an aqueous solution of potassium carbonate, the treatment is preferably performed at a potassium carbonate concentration of 0.05 to 100 g / L and a temperature of 30 to 80 ° C. Thereby, a metal compound film 2 mainly composed of metal carbonate, metal hydroxide and / or metal hydrated oxide is formed on the surface of the base material 1.

Examples of Group II element hydroxides include calcium hydroxide and barium hydroxide. For example, when the metal compound treatment is performed using an aqueous solution of barium hydroxide octahydrate, the treatment is preferably performed at a concentration of barium hydroxide octahydrate of 0.05 to 5 g / L and a temperature of 30 to 80 ° C. .
Further, the salt of a group II element is a salt generated by a group II element and a weak acid, and a metal salt whose aqueous solution shows alkalinity. The salt is mainly formed by combining a weak acid and a Group II element. Examples of the Group II element salt include calcium acetate, strontium acetate, and barium acetate. For example, when the metal compound treatment is performed using an aqueous solution of barium acetate, the treatment is preferably performed at a barium acetate concentration of 0.05 to 100 g / L and a temperature of 30 to 80 ° C. Thereby, a metal compound film 2 mainly composed of a metal carboxylate, a metal hydroxide and / or a metal hydrated oxide is formed on the surface of the metal substrate 1.

  For example, when a metal compound treatment is performed using an aqueous solution of a silicate of a group I element such as sodium orthosilicate, sodium metasilicate, potassium silicate, etc. as a salt of a group I element and a salt of a group II element The formed metal compound film 2 often contains silicate as a main component in addition to hydroxide. An example of such a silicate is a metal silicate (metal is a metal contained in the base material 1). For example, when the metal compound treatment is performed using an aqueous solution of sodium orthosilicate, the concentration of sodium orthosilicate is preferably 0.05 to 100 g / L and the temperature is preferably 30 to 80 ° C. Thereby, a metal compound film 2 mainly composed of metal silicate, metal hydroxide and / or metal hydrated oxide is formed on the surface of the metal substrate 1.

(2) Ammonia, hydrazine, hydrazine derivatives or water-soluble amine compounds Aqueous solutions of ammonia, hydrazine, hydrazine derivatives or water-soluble amine compounds are also alkaline. Even if the base material 1 is immersed in these aqueous solutions, a metal compound film can be formed. In the case of these aqueous solutions, a metal compound film 2 mainly composed of a hydroxide such as a metal hydroxide (metal is a metal contained in the base material 1) is formed on the surface of the base material 1, and Due to the polarity, formation and / or adsorption of an amine complex occurs in the base material 1. However, ammonia does not form a complex with aluminum. Ammonia reacts with, for example, aluminum to form an ammonium salt which is a complex salt with hydroxide. Ammonia, hydrazine, hydrazine derivatives, and water-soluble amines are amine compounds in a broad sense. Other than ammonia and hydrazine, hydrazine, hydrazine carbonate and the like as hydrazine derivatives, and methylamine, dimethylamine, trimethylamine as water-soluble amines, Ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, ethylenediamine, allylamine and the like can be used. For example, when the metal compound treatment is performed using an aqueous solution of hydrazine, it is preferable that the concentration of hydrazine is 0.5 to 100 g / L and the temperature is 30 to 80 ° C. As a result, in addition to the metal compound film 2 containing hydroxide as a main component, the metal compound film 2 is formed on the surface of the metal substrate 1 by forming a complex of metal and hydrazine and / or adsorbing hydrazine.

“(1) Group I element hydroxides, Group I element salts, Group II element hydroxides, Group II element salts” and “(2) Ammonia, hydrazine, hydrazine derivatives or water-solubility described above. Specific examples of “amine compounds” include carbonates such as sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate. By performing a metal compound treatment using an aqueous solution of these carbonates, a metal compound film 2 mainly composed of these carbonates, bicarbonates and / or hydroxides is formed on the surface of the base material 1. . These carbonates, hydrogen carbonates and / or hydroxides may contain a metal carbonate (metal is a metal contained in the base material 1). In addition, a plurality of carbonates other than the metal carbonate contained in the base material 1 may be formed by performing a metal compound treatment in a solution in which different types of metal carbonates are mixed.
For example, when the metal compound treatment is performed using an aqueous solution of sodium carbonate, the aqueous solution is preferably in a range of sodium carbonate concentration: 0.05 to 100 g / L and temperature: 30 to 90 ° C. Thereby, a metal compound film 2 mainly composed of metal carbonate and / or metal hydrated oxide is formed on the surface of the metal substrate 1.

I-2-2. Acid treatment Specific examples of the metal compound treatment solution used for the acid treatment are shown below.
(1) Phosphoric acid, phosphate Phosphoric acid, metal hydrogen phosphate such as zinc hydrogen phosphate, manganese hydrogen phosphate, calcium hydrogen phosphate, metal dihydrogen phosphate such as calcium dihydrogen phosphate salts and, for example zinc phosphate, manganese phosphate, calcium phosphate, sodium calcium phosphate, _-H 2 _PO 4, such as phosphoric acid metal salts such as zirconium phosphate, phosphoric acid and phosphate containing -HPO ₄ or -PO ₄ The metal compound treatment is performed using a salt solution. In this specification, phosphoric acid is a broadly defined acidic phosphoric acid including orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, etc., and a phosphate is a broadly acidic acid such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, etc. It is a concept including a compound of phosphoric acid.

  By using phosphoric acid, the metal compound film 2 mainly composed of a metal phosphate and / or hydroxide is formed on the surface of the base material 1.

  Meanwhile, zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, metal hydrogen phosphate, metal dihydrogen phosphate, metal phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium phosphate By carrying out a metal compound treatment using an aqueous solution of a phosphate (metal salt of phosphoric acid) such as calcium sodium phosphate, zirconium phosphate, vanadium phosphate, zirconium vanadium phosphate, The metal compound film 2 mainly composed of phosphate and / or hydroxide can be formed. The phosphate and / or hydroxide metal compound film 2 may contain a metal phosphate metal salt contained in the base material 1. Moreover, you may form a some phosphate by performing a metal compound process in the solution which mixed the phosphate of the metal from which a kind differs.

  For example, when the metal compound treatment is performed using an aqueous solution of zirconium phosphate, the aqueous solution preferably has a concentration of 1 to 100 g / L and a temperature of 20 to 90 ° C. Other than this, phosphoric acid, zinc phosphate, zinc hydrogen phosphate, manganese phosphate, manganese hydrogen phosphate, hydrogen phosphate metal salt, dihydrogen phosphate metal salt, metal phosphate phosphate, calcium hydrogen phosphate, phosphorus When using an aqueous solution of phosphoric acid and phosphate such as calcium dihydrogen phosphate and calcium phosphate, the aqueous solution preferably has a concentration of 5 to 30 g / L and a temperature of 20 to 90 ° C. It is more preferable that the temperature is from 75 ° C to 75 ° C. On the other hand, when an aqueous solution of zirconium phosphate, vanadium phosphate, or zirconium vanadium phosphate is used, the aqueous solution preferably has a concentration of 0.2 to 2 g / L and a temperature of 30 to 70 ° C. It is more preferable that it is 50 degreeC-70 degreeC.

(2) Carboxylic acid, carboxylate salt A base material 1 is treated with a metal compound using an aqueous carboxylic acid solution such as tannic acid. As a result, a metal compound film mainly composed of a metal salt of carboxylic acid and / or a hydroxide is formed on the surface of the base material 1.

  The metal compound treatment may be performed using an aqueous solution of a metal salt of formic acid, acetic acid, oxalic acid, or succinic acid. In this case, a basic metal compound film 2 having a metal salt and a hydroxyl group on a part of the metal salt is formed on the surface of the base material 1. For example, when the metal compound treatment is performed using an aqueous metal oxalate salt solution, the aqueous solution preferably has a concentration of 0.5 to 100 g / L and a temperature of 30 to 70 ° C.

(3) Fluoride aqueous solution of fluoride such as hydrofluoric acid, sodium fluoride, potassium fluoride, ammonium fluoride, ammonium hydrogen fluoride, silicofluoric acid, ammonium silicofluoride, borohydrofluoric acid, ammonium borofluoride Even if the base material 1 is immersed in the metal compound film, it can be formed. As a result, a metal compound film 2 mainly composed of a metal fluoride and / or a hydroxide such as a metal hydroxide contained in the base material 1 is formed on the surface of the base material 1. For example, when the metal compound treatment is performed using an aqueous ammonium hydrogen fluoride solution, the aqueous solution preferably has a concentration of 1 to 60 g / L and a temperature of 30 to 70 ° C.

(4) Sulfuric acid, sulfate salt Metal compound treatment is performed using sulfuric acid or an aqueous metal salt solution of sulfuric acid such as sodium sulfate, manganese sulfate, calcium sulfate, titanyl sulfate, zirconium sulfate, potassium sulfate, sodium sulfate. When these sulfuric acids and sulfates are used, a metal compound film 2 containing metal sulfate as a main component is formed on the surface of the base material 1.
For example, when the metal salt compound treatment is performed using an aqueous solution of potassium sulfate metal salt, the aqueous solution preferably has a concentration of 0.5 to 30 g / L and a temperature of 30 to 60 ° C.

Among the metal compound treatments shown above, when the base material 1 is any one selected from the group consisting of iron and its alloys, steel, stainless steel, magnesium and its alloys, and copper and its alloys, an acid treatment It is preferable to use the method described in “(1) Phosphoric acid, phosphate”.
When base material 1 is aluminum or an alloy thereof, alkali treatment “(1) Group I element hydroxide, Group I element salt, Group II element hydroxide, Group II element salt” and acidity It is preferable to use the method described in “(1) Phosphoric acid, phosphate” of the treatment.
When the base material 1 is titanium or an alloy thereof, the method described in “(3) Fluoride” of the acid treatment is preferably used.
The reason why the treatment with phosphoric acid and phosphate is preferable is that the phosphate compound formed as the metal compound film 2 has a large polarity and easily binds to silanol formed by hydrolysis of the alkoxysilane of the triazine thiol derivative. This is probably because of this.
The reason why treatment with a hydroxide of a group I element, a salt of a group I element, a hydroxide of a group II element, or a salt of a group II element is preferred is that This is probably because the OH group and the acid group are easily bonded to silanol formed by hydrolysis of the alkoxysilane of the triazine thiol derivative, and the bond strength is high.
The reason why the treatment with fluoride is preferable is considered to be that fluorine of the metal fluoride formed is active, and the alkoxysilane of the triazine thiol derivative is easily bonded to silanol formed by hydrolysis.

  Silanol and metal compound produced by the alkoxysilane-containing triazine thiol derivative in the reactive compound penetrating into the metal compound film 2 to increase the number of sites that react with the metal compound film 2, and the alkoxysilane of the triazine thiol derivative is hydrolyzed. The hydroxyl group, hydrated oxide, ammonium group, phosphoric acid group, carbonic acid group, sulfuric acid group, silicic acid group, carboxylic acid group, or fluoride of the film 2 undergoes a dehydration reaction or a dehalogenation reaction by heat treatment. Join. In this way, a stronger bond can be obtained between the resulting dehydrated silanol-containing triazine thiol derivative coating and the metal compound film 2.

  Further, when the resin 24 is cooled and contracts after the bonding, the metal compound film 2 disperses and absorbs the stress generated between the resin 24 and the metal compound film 2, and the resin 24 is peeled off and the metal compound film 2 is cracked. Has the effect of preventing the occurrence.

  The metal compound treatment using the above solution not only immerses the whole or a part of the base material 1 in the solution (metal compound treatment liquid), but also the whole or a part of the surface of the base material 1. It includes coating with a solution by spraying, coating, etc., or contacting with a solution.

  Therefore, as apparent from the above, the metal compound film 2 does not necessarily have to be formed on the entire surface of the base material 1, and may be formed only on a necessary portion as appropriate.

It goes without saying that the metal compound treatment may be performed by combining two or more methods of forming the metal compound film described above.
That is, the metal compound film may be formed by using a solution obtained by mixing a plurality of solutions used for the metal compound treatment (metal compound treatment liquid). Moreover, after performing a metal compound process using one kind of the solution (metal compound process liquid) used for the metal compound process mentioned above, a metal compound process is further performed using another kind of metal compound process liquid. Also good.

II. Reactive Compound Treatment After the metal compound film 2 is formed on the surface of the base material 1 by the above-described method, the reactive compound layer 3 is applied on the metal compound film 2 and formed.
The reactive compound layer 3 contains an alkoxysilane-containing triazine thiol derivative when applied to the metal compound film 2 (preferably contains 50% or more by mass).
The reactive compound layer 3 may contain, for example, triazine thiol in addition to the alkoxysilane-containing triazine thiol derivative.

The alkoxysilane-containing triazine thiol derivative used for the reactive compound layer 3 may be a known one such as an alkoxysilane-containing triazine thiol metal salt.
That is, it is represented by the general formula shown in the following (Formula 1) or (Formula 2).

R ¹ , R ² and R ³ in the formula are hydrocarbons. R ¹ is, for example, any one of H—, CH ₃ —, C ₂ H ₅ —, CH ₂ ═CHCH ₂ —, C ₄ H ₉ —, C ₆ H ₅ —, and C ₆ H ₁₃ —. R ² is, for example, —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ SCH ₂ CH ₂ —, —CH. ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ —. R ³ is, for example, — (CH ₂ CH ₂ ) ₂ CHOCONHCH ₂ CH ₂ CH ₂ — or — (CH ₂ CH ₂ ) ₂ N—CH ₂ CH ₂ CH ₂ —, in which case N and R ³ is a ring structure.

X in the formula _{is, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, i-C 3 H 7 -, n-C 4 H 9 -, i-C 4 H 9 -, t- One of C ₄ H ₉ —. Y _{is, CH 3 O-, C 2 H} 5 O-, n-C 3 H 7 O-, i-C 3 H 7 O-, n-C 4 H 9 O-, i-C 4 H 9 O- a _{t-C 4 H} 9 O- and alkoxy groups. N in a formula is either 1, 2, or 3 numbers. M is an alkali metal, preferably Li, Na, K or Ce.

  After coating the metal compound film 2, a solution of the alkoxysilane-containing triazine thiol derivative is prepared in order to form a coating of the alkoxysilane-containing triazine thiol derivative on the surface of the metal compound film 2. The solvent to be used is not particularly limited as long as the alkoxysilane-containing triazine dithiol derivative can be dissolved, and water and alcohol solvents correspond to this. For example, water, methanol, ethanol, propanol, carbitol, ethylene glycol, polyethylene glycol, and a mixed solvent thereof can be used. A preferable concentration of the alkoxysilane-containing triazine dithiol derivative is 0.001 g to 20 g / L, and a more preferable concentration is 0.01 g to 10 g / L.

  The base material 1 provided with the metal compound film 2 is immersed in the obtained alkoxysilane-containing triazine dithiol derivative solution. The preferable temperature range of a solution and the more preferable temperature range are 0 degreeC-100 degreeC, and 20 degreeC-80 degreeC, respectively. On the other hand, the immersion time is preferably 1 minute to 200 minutes, more preferably 3 minutes to 120 minutes.

  By this immersion, the alkoxysilane portion of the alkoxysilane-containing triazine thiol derivative is hydrolyzed to become silanol. Therefore, the alkoxysilane-containing triazine thiol derivative after the immersion becomes a silanol-containing triazine thiol derivative, and between the metal compound film 2 It is possible to obtain a chemical bond strength by forming a hydrogen bond and a loose bond.

  Accordingly, the base material 1 having the reactive compound layer 3 including the metal compound film 2 and the silanol-containing triazine thiol derivative coating on the surface can thereby be obtained.

  Then, the base material 1 is heated to 100 ° C. to 450 ° C. for the purpose of drying and dehydration reaction promoting heat treatment. By this heating, the silanol portion of the silanol-containing triazine thiol derivative is dehydrated or dehalogenated with at least one of the hydroxide, carboxylate, phosphate, silicic acid and fluoride contained in the metal compound film 2 described above. Therefore, the silanol-containing triazine thiol derivative is changed to a dehydrated silanol-containing triazine thiol derivative and chemically bonded to the metal compound film 2.

  As a result of this heat treatment, a preferable base material 200 composed of the base material 1, the metal compound film 2 and the reactive compound layer 3 and used for bonding the resin to the surface can be obtained.

  Next, the dehydrating silanol-containing triazine thiol derivative of the reactive compound layer 3 is suitably used as a bonding aid, for example, dimaleimides, in order to further strengthen the bonding force between the dehydrated silanol-containing triazine thiol derivative and the resin. N, N'-m-phenylene dimaleimide, N, N'-hexameethylene dimaleimide and other compounds having binding properties by radical reaction and peroxides such as dicurmyl peroxide and benzoyl peroxide Immerse in a solution containing a radical initiator. After immersion, the preferred substrate 200 is dried and heat-treated at 30 ° C. to 270 ° C. for 1 minute to 600 minutes.

As a result, the dehydrated silanol-containing triazine thiol derivative removes the metal ion of the triazine thiol metal salt (triazine thiol derivative) portion, and the sulfur becomes a mercapto group, and this mercapto group becomes N, N′-m-phenylenedimaleimide. It reacts with one of the two double bonds of maleic acid to form a dehydrated silanol-containing triazine thiol derivative bonded with N, N′-m-phenylene dimaleimide.
The radical initiator has a function of generating a radical by decomposition by heat such as heating performed when molding a resin, opening the other bond of the two double bonds by the maleic acid, and reacting and bonding with the resin.

  Further, if necessary, a solution obtained by dissolving a radical initiator such as a peroxide or a redox catalyst in an organic solvent such as benzene or ethanol is attached to the surface of the reactive compound layer 3 by dipping or spraying. Let it air dry.

  The radical initiator generates radicals by thermal decomposition such as heating performed when molding the resin, opens the other bond of the two double bonds by the maleic acid, or forms a metal salt part of the triazine thiol derivative. It works to react and bond with the resin.

  The dehydrated silanol-containing triazine thiol derivative contained in the metal compound film 2 and the reactive compound 3 of the resin composite material in which the preferable base material 200 and the resin body 24 according to the present invention are integrated is, for example, XPS analysis (X-ray photoelectron spectroscopy analysis). ) To identify the component.

4). Resin The resin 24 may be either a thermoplastic resin or a thermosetting resin as described above.

  Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene (PS), polybutylene, acrylonitrile / styrene (AS), acrylonitrile / butadiene / styrene (ABS), polymethyl methacrylate, vinyl chloride, polyamide (PA), polyacetal, Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polycarbonate (PC), ionomer resin, modified polyphenylene ether, polyphenylene oxide, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, polyether imide, polyamide imide, polyarylate, In addition to polysulfone, polyethersulfone, etc., polymer polymers such as PC / ABS, PBT / ABS, PA / ABS, PC / PS, etc. Lee and the like can be used. The thermoplastic resin also includes a thermoplastic elastomer. Examples of the thermoplastic elastomer that can be used include elastomers such as styrene, polyolefin, polyvinyl chloride, polyurethane, polyester, polyamide, 1,2-polybutadiene, and transisoprene.

  As the thermosetting resin, for example, epoxy, unsaturated polyester, phenol, polyurethane, silicone, diallyl terephthalate, or the like may be used. Further, the thermosetting resin may be one to which a reinforcing material and a filler are added.

1 Base material 2 Metal compound film 2
3 Reactive Compound Layer 3
11 Movable mold (lower mold)
12 cavity (lower mold cavity)
13 Sensor core 14 Temperature sensor 15 Fixed mold (upper mold)
16 cavity (upper mold cavity)
17 Heater 18 Gate 19 Runner 22 Cooling medium guiding path 22a Cooling medium introduction port 24 Resin 26 Void 100 Mold 200 Base material 300 Heating core

Claims (9)

A mold for forming a resin composite by joining the base material and the resin by introducing a resin into the cavity after placing the base material in the cavity,
A temperature sensor for measuring the temperature of the substrate;
A heating source in contact with the substrate to heat the substrate;
A guide path for introducing a cooling medium for cooling the base material into a gap between the heat source and the base material, which is generated when the heat source is separated from the base material;
A mold characterized by containing.   The mold according to claim 1, wherein the heating source is in contact with and separated from a surface of the base material opposite to a surface to be bonded to the resin. Placing the substrate in the cavity of the mold;
Introducing a resin into the cavity after heating the substrate to a predetermined temperature by bringing a heating source into contact with the substrate;
Introducing a cooling medium into a gap between the substrate and the heating source generated by separating the heating source from the substrate to cool the substrate;
The manufacturing method of the resin composite material characterized by including.   The manufacturing method according to claim 3, wherein the heat source is in contact with a surface of the substrate opposite to a surface in contact with the resin. The substrate is
A metal compound film comprising at least one selected from the group consisting of hydroxide, hydrated oxide, ammonium salt, amine compound, carboxylate, phosphate, carbonate, sulfate, silicate and fluoride; ,
A reactive compound layer comprising a water silanol-containing triazine thiol derivative disposed on the demetallized compound film;
The manufacturing method of Claim 3 or 4 characterized by the above-mentioned.   6. The method according to claim 5, wherein the metal compound film contains at least one of a metal hydrated oxide and a hydroxide.   6. The production according to claim 5, wherein the metal compound film includes at least one phosphate selected from the group consisting of a metal hydrogen phosphate, a metal dihydrogen phosphate, and a metal phosphate. Method.   The said resin is a thermoplastic resin, The said predetermined temperature is the range of -50 degreeC-+100 degreeC from the glass transition point or melting | fusing point of the said thermoplastic resin, The any one of Claims 3-7 characterized by the above-mentioned. The manufacturing method as described in.   The said resin is a thermosetting resin, The said predetermined temperature is the range of +0 degreeC-+100 degreeC from the curing temperature of a thermosetting resin, The any one of Claims 3-7 characterized by the above-mentioned. Production method.

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