JP2015081202A - Method for forming resin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a resin film having high adhesion on the surface of an inorganic material without using a silane coupling agent.SOLUTION: Provided is a method for forming a resin film comprising: a step of introducing an amino group into the surface of an inorganic material; and a step of forming a thermosetting resin or a thermoplastic resin or a resin film including resin components made of their mixture on the surface of the inorganic material, the resin components have a molecular structure selected from carboxyl groups, carbonyl groups, acid anhydrides and ester groups.

Description

  The present invention relates to a method for forming a resin film, and the present invention particularly relates to a method for forming a resin film on an inorganic material.

  In order to strengthen the bond between the inorganic material and the resin, it is generally known to add a silane coupling agent to the resin (for example, Non-Patent Document 1).

  On the other hand, a technique for obtaining a nanocomposite resin by introducing an amino group with high efficiency on the surface of an inorganic filler without using a silane coupling agent is also known (for example, Patent Document 1).

JP 2012-171975 A

Silane coupling agent (Toray Dow Corning Co., Ltd. catalog, issued in October 2008)

  The resin film formed on the surface of the inorganic material in which the resin and the inorganic material are adhered to each other with a silane coupling agent may have sufficient adhesion and durability depending on the purpose of use. However, when a resin film formed on the surface of an inorganic material is used as, for example, an electronic material or an optical material, the resin film in which the resin and the inorganic material are simply brought into close contact with each other by a silane coupling agent is subjected to a thermal load. Under certain conditions, characteristics such as long-term durability may not be sufficiently satisfied.

In particular, when a silane coupling agent is used and a resin film is formed on alumina (Al ₂ O ₃ ) or magnesia (MgO) as an inorganic material, these inorganic materials are particularly effective for the silane coupling agent. May be difficult to obtain. That is, peeling often occurs at the interface between an inorganic material made of Al ₂ O ₃ or MgO and a resin, and therefore, when a resin film formed on the surface of an inorganic material is used as an electronic material or an optical material. However, there are problems that desired properties of the mechanical properties and thermal conductivity may not be obtained or it may be difficult to control.

  On the other hand, when an attempt is made to directly form a resin film on an untreated inorganic material without using a silane coupling agent, the resin film is weak because the adhesion at the interface between the inorganic material and the resin film is weak. Even after the formation, even if the interface between the inorganic material and the resin film is in close contact, peeling may occur at the interface after long-term use. As a result, characteristic fluctuations and deterioration of the electronic material or the optical material are caused, and there is a case where a problem occurs in the long-term reliability of these electronic material or optical material.

  In view of such a problem, if a resin film having high adhesiveness can be formed on an inorganic material without using a silane coupling agent, it is expected that it can be used for a wide range of applications. That is, an object of the present invention is to obtain a resin film on an inorganic material with improved adhesion without using a sila coupling agent.

  A hydroxyl group usually exists on the surface of the inorganic material. When a silane coupling agent is used, the hydroxyl group reacts with the silane coupling agent to bond. However, as a result of the study by the present inventors, a molecule selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group without using a silane coupling agent by replacing the surface hydroxyl group of the inorganic material with an amino group. The present invention has been completed in consideration of forming a film of a thermosetting resin or a thermoplastic resin having a structure on an inorganic material.

  That is, according to one embodiment of the present invention, there is provided a resin film formation method comprising a step of introducing an amino group on the surface of an inorganic material and a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof. Forming a resin film on the surface of the inorganic material, and the resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group It is.

In the resin film forming method, it is preferable that the inorganic material contains at least one selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN as a main component.

In the resin film forming method, the inorganic material is an inorganic film on the surface of which a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN is formed. A material is preferred.

According to another embodiment of the present invention, there is provided a resin film forming method, wherein the inorganic material surface is selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN. A step of forming a coating comprising the above as a main component, a step of introducing an amino group on the surface of the coating, a resin film comprising a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof, The resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group, a main component of the inorganic material, and a main component of the coating This is a resin film forming method in which the components are different.

  In the resin film forming method, it is preferable that the inorganic material on which the coating film is formed contains at least one selected from BN, CaF, and MgF as a main component.

  In the resin film forming method, the inorganic material is preferably a substrate.

  In the resin film forming method, the resin component is preferably a polyamide resin.

  In the resin film forming method, the resin component is preferably an epoxy resin.

  According to the resin film forming method of the present invention, a resin film having high adhesion can be formed on an inorganic material. In particular, without using a silane coupling agent, a highly reliable resin film having heat resistance can be formed by a simple and economical method. In addition, the resin film formed on the inorganic material as described above is useful as an electronic material or an optical material that requires reliability such as durability.

[First Embodiment]
According to the first embodiment of the present invention, there is provided a resin film forming method comprising: introducing an amino group into an inorganic material surface; and a resin component comprising a thermosetting resin, a thermoplastic resin, or a mixture thereof. And forming the resin film on the inorganic material, wherein the resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group.

In the first embodiment, the inorganic material only has to be a metal oxide or metal nitride as a main component. For example, SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , AlN. It is preferable that the main component is one or more selected from the above, but is not limited thereto. This is because inorganic materials containing these compounds as the main component have a great effect of improving adhesion by introducing amino groups. The metal oxide usually has an OH group on the surface. Moreover, since the surface of AlN is usually oxidized to become Al ₂ O ₃ , it similarly has OH on the surface.

  The shape of the inorganic material may be, for example, a plate-like, rod-like, particle-like or block-like material, and its dimensions and thickness are not particularly limited. More preferably, the inorganic material includes a substrate. For example, a substrate in which these inorganic material films are formed on a substrate of an electronic material such as a wafer, a substrate of an optical material, a ceramic substrate, or a semiconductor substrate such as silicon can be exemplified, but the invention is not limited thereto. When a substrate of an electronic material such as a wafer is used as the inorganic material of this embodiment, it is preferable that the substrate is not patterned.

  In the present invention, the surface of the inorganic material means at least a part of the surface of the inorganic material and a target surface to which a resin film to be described in detail later is attached. Therefore, it may be the entire surface of the inorganic material or a part of the surface of the inorganic material. Further, when the inorganic material is composed of a plurality of surfaces, it may be only one surface or two or more desired surfaces. In the second embodiment to be described later, the inorganic material is an inorganic material provided with a film. In that case, the surface of the inorganic material into which amino groups are introduced is at least the surface of the film to which the resin film is attached. Let's say some surface.

  The resin film forming method according to the present embodiment includes a first step of introducing an amino group on the surface of an inorganic material and a thermosetting resin having a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. And a second step of forming a resin film containing a resin component made of any one of thermoplastic resins or a mixture thereof on the inorganic material into which the amino group has been introduced without using a silane coupling agent. . Therefore, in this embodiment, the component of the resin film does not contain a silane coupling agent, and the inorganic material is not treated with the silane coupling agent.

  First, the 1st process which introduce | transduces an amino group into an inorganic material surface is demonstrated. Examples of the method for introducing an amino group on the surface of the inorganic material include a method of substituting a hydroxyl group that is usually present on the surface of the inorganic material with an amino group. The method includes a step of heat-treating the surface of the inorganic material and a heat-treated inorganic material. Contacting with an amination reagent.

  The step of heat-treating the surface of the inorganic material is a step of heating the inorganic material usually for about 10 to 120 minutes in a heating furnace at 1000 ° C. to 1200 ° C., for example. By this step, the hydroxyl group on the surface of the inorganic material is removed, and the introduction of the amino group is facilitated. The step of heat-treating the surface of the inorganic material can also be performed by laser light irradiation. However, the heat treatment step is not limited to the heating temperature, time, and method shown here, and can be appropriately determined depending on the composition and material of the inorganic material.

  After the above heat treatment step, it is preferable to put in another heating furnace set to the amino group introduction temperature and perform the subsequent amino group introduction treatment after reaching the desired temperature. This is to prevent recombination of hydroxyl groups after the heat treatment step. The set temperature of another heating furnace is, for example, about 100 to 300 ° C., and preferably about 200 to 260 ° C., but is not limited to this temperature range.

  After bringing the inorganic material to a desired temperature in another heating furnace, a step of bringing the heat-treated inorganic material into contact with the amination reagent is performed. Such a step is preferably carried out under a condition in which the hydroxyl group on the surface of the inorganic material is reduced as much as possible, that is, in a glove box or the like in a dry atmosphere using a desiccant.

  The amination reagent may be ammonia itself. When ammonia itself is used as the amination reagent, the step of bringing the heat-treated inorganic material into contact with the amination reagent is preferably performed at a temperature of 20 to 500 ° C. for 10 to 180 minutes. At this time, the vapor pressure (partial pressure) of ammonia is preferably 0.3 to 1 atm. Alternatively, an ammonia generator can also be used as the amination reagent. The ammonia generator is one that generates ammonia by heating as necessary and contacting with an appropriate catalyst as necessary to decompose, and examples thereof include dimethylamine, urea, and ammonium chloride. Even when an ammonia generator is used, the partial pressure of the generated ammonia is preferably within the above range.

  The amination reagent does not contain an amine-based silane coupling agent. The ammonia finally produced as an amination reagent in this application is preferably dried and used so as not to promote silanol group production on the surface of the inorganic material when water vapor is contained. The desiccant is preferably a basic desiccant. For example, a physical desiccant such as aluminum oxide, zeolite or molecular sieve, or a chemical desiccant such as sodium hydroxide, potassium hydroxide or calcium oxide is used alone. Alternatively, two or more kinds can be used in appropriate combination.

  After the step of contacting with the amination reagent, it is confirmed, for example, by infrared spectroscopy or time-of-flight secondary ion mass spectrometry (TOF-SIMS) that amino groups are introduced on the surface of the inorganic material. can do. Immediately after the treatment, an inorganic material obtained by treatment in this way is coated with a composition containing a resin component comprising a thermosetting resin, a thermoplastic resin, or a mixture thereof to form a film. However, when the film is not formed immediately, the inorganic material may be stored in a desiccator in an inert gas atmosphere such as nitrogen.

  Next, a resin film containing a resin component made of either a thermosetting resin or a thermoplastic resin or a mixture thereof is formed on the inorganic material into which the amino group is introduced without using a silane coupling agent. The second step will be described.

  The resin constituting the resin film may be either a thermosetting resin or a thermoplastic resin as long as it has one or more molecular structures selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. It may be a mixture thereof. In the present specification, a thermosetting resin, a thermoplastic resin, or a mixture thereof composed of a thermosetting resin main component, a curing agent, and optionally a curing accelerator is collectively referred to as a resin component.

  As the thermosetting resin, those having a relatively high glass transition temperature [Tg] and a low dielectric constant of about 4 to 7 can be used. Examples of preferred thermosetting resins include, but are not limited to, epoxy resins, polyimide resins, and unsaturated polyester resins. When the resin component is a thermosetting resin, the resin component includes a thermosetting resin main component, a curing agent, and a curing accelerator as necessary. A curing accelerator can be effectively used to control the curing reaction.

  The main component of the epoxy resin which is a preferable thermosetting resin is not particularly limited as long as it has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. Even if the epoxy resin main component itself does not have these structures, it can form a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group in the course of the crosslinking reaction with the curing agent. I just need it. For example, bifunctional epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, naphthalene type epoxy resin Polyfunctional epoxy resins such as biphenyl type epoxy resins and dicyclopentadiene type epoxy resins can be used alone or in combination. In particular, a polymer compound after curing that contains a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group in the molecular structure of the epoxy resin main agent itself or that is obtained by crosslinking with a curing agent. From the viewpoint of containing a large amount, for example, a polyfunctional epoxy resin is preferable as the epoxy resin main component.

  The curing agent for the thermosetting resin can be selected in relation to the main component of the thermosetting resin. For example, when an epoxy resin main agent is used as the thermosetting resin main agent, those generally used as an epoxy resin curing agent can be used. In particular, as the curing agent, an acid anhydride curing agent can be preferably used. Specifically, acid anhydride curing agents such as methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and isomers and modified products thereof are used. be able to. Moreover, a hardening | curing agent can use one type of these individually, or can mix and use 2 or more types. In particular, these curing agents are preferable in that a molecular structure such as a carboxyl group or an ester group can be introduced into the polymer compound after curing.

  Curing accelerators include imidazoles such as 2-ethyl-4-methylimidazole, tertiary amines such as benzyldimethylamine, aromatic phosphines such as triphenylphosphine, and Lewis acids such as boron trifluoride monoethylamine. Boric acid esters and the like can be used, but are not limited thereto.

  The blending ratio of the curing agent can be determined from the epoxy equivalent of the epoxy resin main component and the amine equivalent or acid anhydride equivalent of the curing agent. Similarly, when using a thermosetting resin main component other than the epoxy resin, the blending ratio can be determined based on the reaction equivalent of each resin main component and the reaction equivalent of the curing agent. Moreover, when using a hardening accelerator, it is preferable that the mixture ratio of a hardening accelerator shall be 0.1-5 mass% when the mass of an epoxy resin main ingredient is 100%.

  When the resin component is a thermoplastic resin, a polyamide resin can be used as a preferable thermoplastic resin. This is because the carboxyl group structure at the terminal of the polymer compound constituting the polyamide resin forms a bond with the amino group introduced on the surface of the first inorganic filler and the second inorganic filler. However, the thermoplastic resin is not limited to the polyamide resin as long as it has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. A resin film containing a polyamide resin as a main component is particularly advantageous in that it has high chemical resistance and oil resistance.

  The resin film according to the present embodiment may be composed of only the above resin components and may not include other components. Alternatively, as further optional components, conventionally known reinforcing fibers such as glass fiber, carbon fiber, graphite fiber, and aramid fiber may be included. In addition, other additives which do not impair the physical properties of the resin film within the scope of the present invention may be included, but a silane coupling agent is not included.

  In the formation of the resin film, when the resin component is a thermosetting resin, a resin composition obtained by mixing a main agent and a curing agent, and optionally a curing accelerator, is obtained by introducing an amino group of an inorganic material. It can apply | coat so that it may touch the surface of this. Therefore, it is excluded from the present embodiment that a resin film is formed on a surface of an inorganic material into which amino groups are introduced via a layer of a silane coupling agent or other composition. In the case of a thermoplastic resin, the thermoplastic resin can be dispersed in an appropriate solvent and applied in the same manner. When the inorganic material is in the form of a substrate, it can be applied using a spin coating method.

  Then, optionally, a heat curing step for curing the thermosetting resin is performed. Here, according to a normal method, the applied resin film is heated and cured at a temperature equal to or higher than the curing temperature of the thermosetting resin. In the case of an epoxy resin, for example, heating is preferably performed at 100 to 250 ° C. for about 1 to 20 hours. In addition, when using a thermoplastic resin as a resin component, a heat-hardening process is unnecessary.

According to the resin film formation method by 1st Embodiment, a resin film can be formed on an inorganic material with high adhesiveness by a simple and economical method. The resin film on the inorganic material thus obtained can achieve long-term durability even when used under high temperature conditions. In particular, the inorganic material is a material mainly composed of at least one selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN, so that a carboxyl group, a carbonyl group, an acid Adhesion with a resin component having a molecular structure selected from an anhydride and an ester group can be further improved.

[Second Embodiment]
According to a second embodiment of the present invention, there is provided a resin film forming method comprising the steps of introducing an amino group on the surface of an inorganic material, and a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof. Forming a resin film on the surface of the inorganic material, wherein the resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. In particular, the inorganic material is an inorganic material on the surface of which a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN is formed. .

In the second embodiment, the inorganic material is an inorganic material on the surface of which a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN is formed. It is characterized by being. The inorganic material may be any inorganic material as long as a film mainly composed of these inorganic compounds is formed on the surface. In particular, it is preferable that the inorganic material having a film mainly composed of these inorganic compounds formed on the surface thereof is mainly composed of fluorides such as BN, CaF, and MgF, or a combination thereof. . Also, coating the inorganic material constituting an inorganic material formed on its surface, the coating is long as if different kinds of the compound, for example, inorganic material film is subjected is, SiO 2, _ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , AlN, an inorganic material whose main component is selected from the group consisting of SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ Another inorganic material containing as a main component one or more selected from MgO, TiO ₂ and AlN may be used.

  In this embodiment, “the film is formed on the surface” means that the portion where the film is formed may be the entire surface of the inorganic material or a part of the surface of the inorganic material. Moreover, it is sufficient for the coating to provide a reaction field sufficient to introduce amino groups, and the thickness is not particularly limited, but can be, for example, 5 nm to 10 μm.

The inorganic material having a film formed on the surface may be commercially available, or can be appropriately manufactured by a person skilled in the art by a known method. A vapor deposition method, a sputtering method, and a laser ablation method are used to form an arbitrary inorganic material having a coating mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ and AlN. It can prepare by.

Accordingly, in one aspect of the second embodiment, a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN is formed on the surface of the inorganic material. It is possible to include a step of Such a step can be performed before the first step of introducing an amino group on the surface of the inorganic material. Therefore, in an aspect of the second embodiment, the resin film forming method mainly includes at least one selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN on the surface of the inorganic material. A step of forming a film as a component, a step of introducing an amino group into the surface of the film, and a resin film comprising a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof. Forming.

In the second embodiment, the first step of introducing an amino group on the surface of the inorganic material includes at least one selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN as a main component. An amino group may be introduced into the coating film, and this can be performed in the same manner as the first step of the first embodiment. Further, the second step of forming a resin film on the inorganic material film into which the amino group has been introduced can also be carried out in the same manner as the second step of the first embodiment.

According to the second embodiment, a coating mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN is formed on an arbitrary inorganic material. By forming and introducing an amino group to the surface of the coating, the resin component having a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group is closely attached to the inorganic material, as in the first embodiment. Thus, the resin film can be formed. In addition, forming a film in this way is advantageous in that a strong resin film can be attached to various inorganic materials.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples do not limit the present invention.

[Example 1]
In Example 1, an alumina substrate was used as the inorganic material, and first, a step of introducing amino groups into the alumina substrate was performed. An alumina substrate having a diameter of 100 mm and a thickness of 0.5 mm was used. This alumina substrate was placed in a quartz tray and placed in a baking furnace maintained at about 1100 ° C. One hour later, the alumina substrate was taken out together with the tray, and then left to stand in a baking furnace maintained at 250 ° C. for about 2 hours. Thereafter, the alumina substrate was moved into a container (capacity: 30 L) in an ammonia atmosphere. An ammonia atmosphere was formed by putting 25% ammonia water in a glass container into the container. At this time, the temperature of the container in the ammonia atmosphere was room temperature. The vapor pressure (partial pressure) of ammonia was about 0.5 atm. After standing for 150 minutes, the alumina substrate was taken out. By this step, the amino group was introduced into the alumina substrate by replacing the hydroxyl group of the alumina substrate with an amino group.

  Thereafter, a polyamide resin was applied on the alumina substrate. Nylon 66 manufactured by Toray Industries, Inc. was used as the polyamide resin. This nylon 66 was dispersed to about 10% with a solvent (for example, trifluoroethanol), and applied to an alumina substrate with a thickness of about 2 μm using a spin coater. After application, it was dried at room temperature. The alumina substrate was not coated with a silane coupling agent, and the silane coupling agent was not mixed with the polyamide resin.

[Comparative Example 1-1]
Nylon 66 was applied to an untreated alumina substrate in the same manner as in Example 1 without carrying out the step of introducing an amino group into the alumina substrate, and this was designated as Comparative Example 1-1.

[Comparative Example 1-2]
A silane coupling agent was applied to the alumina substrate. As the silane coupling agent, aminosilane-based KBP-40 made by Shin-Etsu Silicone was diluted to 20% with ethanol, and the diluted solution was dropped onto an alumina substrate so as to be 1 L / m ² and treated with a spin coater. . Nylon 66 was applied from the top of the silane coupling agent in the same manner as in Example 1, and this was designated as Comparative Example 1-2.

[Example 2]
In the same manner as in Example 1, the amino group was introduced into the alumina substrate by replacing the hydroxyl group of the alumina substrate with an amino group. Thereafter, an epoxy resin was applied on the alumina substrate. A bisphenol A type epoxy resin (product number: 828, manufactured by Mitsubishi Chemical Corporation) was used as the epoxy resin main component. An acid anhydride curing agent (product number: 307, manufactured by Mitsubishi Chemical Corporation) was used as the curing agent. The resin composition was 110 parts by mass of the curing agent with respect to 100 parts by mass of the epoxy resin main agent. After the mixture of the epoxy resin main agent and the curing agent was stirred, the mixture was applied on an alumina substrate to a thickness of about 2 μm using a spin coater. In the curing treatment after coating, the film was held at 80 ° C. for 3 hours (preliminary heating) and then held at 150 ° C. for 6 hours. The alumina substrate was not coated with a silane coupling agent, and the epoxy resin was not mixed with the silane coupling agent.

[Comparative Example 2-1]
An epoxy resin was applied to an untreated alumina substrate in the same manner as in Example 2 without carrying out the step of introducing an amino group into the alumina substrate, and this was designated as Comparative Example 2-1.

[Comparative Example 2-2]
A silane coupling agent was applied to the alumina substrate. As the silane coupling agent, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (product number: KBM-303, manufactured by Shin-Etsu Silicone) was used in an amount of 2% by mass based on the amount of the epoxy resin main component. From the top of the silane coupling agent, an epoxy resin was applied in the same manner as in Example 2, and this was designated as Comparative Example 2-2.

[Example 3]
In Example 3, a CaF substrate was used as the inorganic material, and first, a step of forming an alumina coating on the surface of the CaF substrate was performed. A CaF substrate having a diameter of 100 mm and a thickness of 0.5 mm was used. The alumina coating was formed to a thickness of 1 μm by the CVD method. Next, an amino group was introduced into the surface of the alumina coating formed on the inorganic substrate. The subsequent steps were the same as in Example 1.

[Comparative Example 3-1]
Nylon 66 was applied to the CaF substrate on which the untreated alumina coating was formed on the surface without performing the step of introducing amino groups on the CaF substrate on which the alumina coating was formed on the surface in the same manner as in Example 1. This was designated as Comparative Example 3-1.

[Comparative Example 3-2]
A CaF substrate having an alumina coating formed on the surface thereof was treated with a silane coupling agent in the same process as in Comparative Example 1-2, and nylon 66 was applied thereto, which was designated as Comparative Example 3-2.

[Example 4]
In Example 4, an inorganic material having an alumina film formed on CaF was used as in Example 3, and an epoxy resin was used as the resin material. The epoxy resin treatment process was the same as in Example 2.

[Comparative Example 4-1]
An epoxy resin is applied to the CaF substrate on which the untreated alumina coating is formed on the surface without performing the step of introducing an amino group on the CaF substrate on which the alumina coating is formed, as in Comparative Example 2-1. This was designated as Comparative Example 4-1.

[Comparative Example 4-2]
A CaF substrate with an alumina coating formed on the surface was treated with a silane coupling agent in the same process as in Comparative Example 2-2, and an epoxy resin was applied thereto, which was designated as Example 4-2.

[Test example]
[Tensile test: Example 1 and Comparative Examples 1-1 and 1-2]
A tensile test of the nylon resin film was performed on the alumina substrate formed with the nylon resin film prepared in Example 1 and Comparative Examples 1-1 and 1-2. A sample was cut into 10 mm □, a tensile test was performed using a stud tensile peel strength measurement (device name: Romulus, manufactured by QUAD GROUP), and the presence or absence of interface peeling was visually confirmed. The number of test samples was 20 each. In Comparative Example 1-1, interface peeling occurred in all 20 samples, and in Comparative Example 1-2, 10 samples occurred. On the other hand, in Example 1, interfacial peeling did not occur in all 20 pieces, and cohesive failure occurred on the nylon resin side.

[Tensile test: Example 2 and Comparative Examples 2-1 and 2-2]
About the alumina substrate which formed the epoxy resin film prepared in Example 2 and Comparative Examples 2-1 and 2-2, the tensile test of the resin film was implemented similarly to the sample of Example 1. The number of test samples was 20 each. Interfacial peeling occurred in all 20 samples in Comparative Example 2-1, and 10 samples in Comparative Example 2-2. On the other hand, in Example 2, no interface peeling occurred in all 20 pieces.

[Tensile test: Example 3 and Comparative Examples 3-1 and 3-2]
For the alumina substrate formed with the nylon resin film prepared in Example 3 and Comparative Examples 3-1 and 3-2, the tensile test of the resin film was performed in the same manner as the sample of Example 1. The number of test samples was 20 each, and interface peeling occurred in all 20 samples in Comparative Example 3-1, and in 10 samples in Comparative Example 3-2. On the other hand, in Example 3, no interface peeling occurred in all 20 pieces.

[Tensile test: Example 4 and Comparative Examples 4-1 and 4-2]
About the alumina substrate which formed the epoxy resin film prepared in Example 4 and Comparative Examples 4-1 and 4-2, the tensile test of the resin film was implemented similarly to the sample of Example 1. The number of test samples was 20 each. Interfacial peeling occurred in all 20 samples in Comparative Example 4-1, and 10 samples in Comparative Example 4-2. On the other hand, in Example 4, no interface peeling occurred in all 20 pieces.

[Heat cycle test: Example 2 and Comparative Examples 2-1 and 2-2]
The heat cycle test was conducted for the purpose of confirming the presence or absence of interface peeling between the epoxy resin film after long-term use and the alumina substrate. The low temperature side was held at −40 ° C. for 30 minutes, and the high temperature side was held at 150 ° C. for 30 minutes as one cycle. However, the sample manufactured by the method of Comparative Example 2-1 was not subjected to the heat cycle test because interfacial peeling occurred in all 20 samples in the tensile test. In Comparative Example 2-2, the heat cycle test was performed only on 10 samples in which interface peeling did not occur in the tensile test.

  After the heat cycle test, a tensile test was performed in the same manner as described above. The number of tests of the sample manufactured by the method of Example 2 was 20. In the sample manufactured by the method of Comparative Example 2-2, interfacial peeling occurred in all 10 samples. On the other hand, in the samples manufactured by the method of Example 2, no interfacial peeling was observed in all 20 samples.

[Heat cycle test: Example 4 and Comparative Examples 4-1 and 4-2]
A heat cycle test was conducted in the same manner as in Examples 2 and 2-1, 2-2. However, Comparative Example 4-1 did not perform a heat cycle test because interfacial peeling occurred in all samples in the tensile test.
After the heat cycle test, a tensile test was performed in the same manner as described above. In the sample manufactured by the method of Comparative Example 4-2, interfacial peeling occurred in all 10 samples. On the other hand, in the sample manufactured by the method of Example 4, no interfacial peeling was observed in all 20 samples.

  The occurrence of interfacial debonding by the heat cycle test indicates that the characteristics are likely to change with long-term use. Therefore, it was shown that the resin films of Comparative Examples 2-2 and 4-2 have a problem in long-term reliability. On the other hand, in Example 2 and Example 4, generation | occurrence | production of interface peeling was not seen by the tension test after a heat cycle test. That is, it was found that the epoxy resin film formed by the resin film forming method of the present invention does not peel off after long-term use, and long-term reliability is obtained.

  The present invention can be applied to all fields in which a resin having a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group is applied to an inorganic material such as glass or an alumina substrate.

Claims (8)

Introducing an amino group into the surface of the inorganic material;
Forming a resin film comprising a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof on the surface of the inorganic material,
A resin film forming method, wherein the resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group. _{2. The} method of forming a resin film according to claim 1, wherein the inorganic material is mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN. 2. The inorganic material is an inorganic material having a surface formed with a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN. Or the resin film formation method of 2. Forming a film mainly composed of one or more selected from SiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , and AlN on the surface of the inorganic material;
Introducing an amino group into the coating surface;
Forming a resin film comprising a resin component comprising a thermosetting resin or a thermoplastic resin, or a mixture thereof on the surface of the coating film,
A resin film forming method, wherein the resin component has a molecular structure selected from a carboxyl group, a carbonyl group, an acid anhydride, and an ester group, and a main component of the inorganic material is different from a main component of the film.   The method for forming a resin film according to claim 3 or 4, wherein the inorganic material on which the coating film is formed contains at least one selected from BN, CaF, and MgF as a main component.   The resin film forming method according to claim 1, wherein the inorganic material is a substrate.   The method for forming a resin film according to claim 1, wherein the resin component is a polyamide resin.   The resin film forming method according to claim 1, wherein the resin component is an epoxy resin.