JP7212485B2 - Composites, hard materials, and methods of making hard materials - Google Patents

Description

The present invention relates to composites, in particular composites containing epoxy resins, hard materials, and methods of making hard materials.

In general, epoxy resins are excellent in mechanical properties, heat resistance, adhesion to various materials, chemical resistance, and molding dimensional accuracy, so they are required not only for structural materials but also for high durability. It is used in a wide range of fields such as electronic equipment. In particular, epoxy resins have been used for many years as adhesives and binders for bonding various materials.

For example, in applications where repeated loads are applied over a long period of time, epoxy resins are characterized by network polymers that prevent intermolecular slippage and exhibit high resistance to stress relaxation and fatigue fracture, resulting in high adhesion and reliability. It is expected to be used in industrial fields that require high performance. Typically, there is a possibility that the use of epoxy resins will expand as adhesives for dissimilar materials such as resins, metals, and ceramic materials used in automobile structures.

On the other hand, cured epoxy resins are generally said to have problems in mechanical properties and environmental resistance. A typical example that requires heat resistance and impact resistance is a binder for grindstones.

Hard materials typified by grindstones (resinoid grindstones) generally use hard ceramic particles such as diamond as abrasive grains. After binding the abrasive grains with a binder resin, they are typically molded into a circular shape and hardened, and then rotated at high speeds for use in cutting, grinding, or polishing hard materials such as rock, metal, or ceramics.

As mentioned above, when cutting, grinding, or polishing, hard materials such as grindstones are exposed to severe friction and wear environments, so they are required to have adhesive strength and toughness to maintain bonding even at high temperatures. Desired. In addition, it has impact resistance that does not chip or break even if it comes in contact with a hard material with a momentary strong force while rotating at high speed, and distortion that occurs in the radial and circumferential directions in the grinding wheel due to the strong centrifugal force of high-speed rotation. Therefore, the grindstone is required to be flexible enough not to be deformed and broken under conditions of repeated load as the temperature rises (Non-Patent Document 1).

In particular, in recent years, the dimensional accuracy required for cutting, grinding, or polishing has increased. Furthermore, the usage environment for hard materials represented by grinding wheels is even more severe, such as cutting, grinding, or polishing strong and sticky materials such as high-strength materials that are composites of ceramics and metals or resins, or CFRP. It has become. On the other hand, with hard materials such as grindstones, abrasive grains fall off moderately during the process of cutting, grinding, or polishing, preventing excessive temperature rise and excessive load from occurring, leading to the destruction of the entire grindstone. There is a need for a technology to prevent Binder resins are required not only to have the above-mentioned advanced mechanical properties, but also to have special functions such as being able to locally and moderately break down when subjected to a load above a certain level.

Polyimide resin (Patent Document 1), phenol resin (Patent Document 2), urethane resin (Patent Document 3), and epoxy resin (Patent Documents 4 and 5) have been disclosed as binder resins for grindstones.

JP 2004-09159 A JP-A-57-27667 Japanese Patent Laid-Open No. 04-249514 JP-A-53-066090 Japanese Patent Application Laid-Open No. 2004-269680

Hideo Inoue, "Estimation of Centrifugal Fracture Strength of Vitrified Grinding Wheel", Seishin Kikai, Vol. 37, No. 2, 1971, 105-111

However, as described above, cured epoxy resins are generally very difficult materials to achieve both mechanical properties and environmental resistance such as weather resistance or heat resistance. In particular, when an attempt is made to increase the heat resistance of the cured product, there arises a problem that the impact resistance of the cured product is impaired due to embrittlement.

On the other hand, polyimide resin has a property of high heat resistance, but poor adhesion to ceramics and the like. Phenolic resins have high hardness, but poor flexibility, making it difficult to obtain strength and flexibility in a high-temperature environment. Furthermore, although polyurethane is excellent in flexibility, it is difficult to obtain toughness.

As mentioned above, when conventional resin materials are used, high mechanical reliability and high molding dimensional accuracy are required in harsh environments. In addition to toughness and high heat resistance, there is no composite material (typically a binder resin) that has flexibility and appropriate detachability at present, and includes the composite material and the composite material. It can be said that the research and development of hard materials are still halfway through.

INDUSTRIAL APPLICABILITY The present invention can greatly contribute to providing a composite material or hard material that can solve at least one of the following technical problems (1) to (4).
(1) Realize high bonding strength to ceramics and the like.
(2) Exhibits high mechanical strength, especially at high temperatures.
(3) exhibit toughness, impact resistance, and/or flexibility even under rubbing and/or abrasive environments;
(4) Overall destruction can be suppressed or prevented by reducing the excessive load by appropriately falling off or the like.

The present inventor focused on the relationship between the unique structure and function of epoxy resin. Specifically, the present inventors have found solid epoxy resins with little deterioration in mechanical strength at relatively high temperatures (that is, high heat resistance), toughness and high impact resistance, and various materials. The inventors have focused on a liquid epoxy resin having good adhesiveness and flexibility. In addition, as a result of the inventor's intensive research and repeated trial and error, the above technical problem is to form a composite material obtained by mixing the following (x) and (y) I learned that it can contribute to the solution of
(x) the aforementioned solid epoxy resin (also referred to as “first epoxy resin (a1)”) and a solid curing agent that is molecularly highly crosslinkable (also referred to as “first curing agent (a2)”); A powdery solid resin (solid powdery resin) in a semi-cured state (hereinafter also referred to as “B stage”) using
(y) the aforementioned liquid epoxy resin (also referred to as "second epoxy resin ( b1 )") and a liquid curing agent having moderate flexibility in molecular structure ("second curing agent (b2)"); Also called.) Liquid resin formed using

In addition, the present inventors have found that by using the composite material described above, when heat is applied to the composite material, the solid powder segment and the liquid segment are cured separately, so to speak, in the composite material , can express the excellent functions of each segment. It should be noted that when the solid powdery resin and the liquid resin are mixed, the existence form of the solid powdery resin is the above-mentioned semi-cured state (B stage), which is the epoxy resin (a1) on the solid powdery resin side. The present inventors believe that this helps the curing agent (a2) to exist without being too far apart. In other words, the solid powdery resin is mixed with the liquid resin to the extent that the influence of the second epoxy resin (b1) and / or the second curing agent (b2) can be suppressed. The present inventors believe that a state in which the appropriate independence of is maintained can contribute to the exhibition of the technical effects of the above-described composite material. An example of the possible influence of the second epoxy resin (b1) and/or the second curing agent (b2) is the solid powdery form of the second epoxy resin (b1) and/or the second curing agent (b2). Intrusion into the resin or weakening of the relationship between the epoxy resin (a1) and the curing agent (a2) described above due to the second epoxy resin (b1) and/or the second curing agent (b2).

As a result, the present inventors found that when the composite material described above is used as a binder resin, when the mixture obtained by mixing the composite material and inorganic particles is cured by heating, severe friction and / or wear occurs. The inventors have found that it is possible to realize a hard material that can solve at least a part of the above technical problems required under the environment. The present invention was created from such a point of view.

One composite material of the present invention comprises a solid powdery resin (A) that is solid at 40° C., containing a first epoxy resin (a1) and a first curing agent (a2), and a second epoxy resin (b1) and a liquid resin (B) that is liquid at 4° C. and a second curing agent (b2).

According to this composite material, for example, when heat is applied, a solid powder segment typified by a solid powdery resin and a liquid segment typified by a liquid resin are individually cured, so that in the composite material, each The superior function of the segment can be expressed. Specifically, in the composite material, the excellent functions of a solid epoxy resin having toughness and high impact resistance and the liquid epoxy resin having adhesion to various materials and flexibility are used. It can significantly express the excellent functions it has.

Also, one hard material of the present invention contains inorganic particles and the composite material described above.

According to this hard material, by containing the inorganic particles and the above-described composite material, at least one of the following technical effects that can withstand use in high-precision or high-load environments can be achieved.
(1) Exhibits high mechanical strength, especially at high temperatures.
(2) exhibit toughness, impact resistance, and/or flexibility even under rubbing and/or abrasive environments;
(3) Overall destruction can be suppressed or prevented by reducing the excessive load by appropriately falling off or the like.
As a result, this hard material is suitable for abrasives, cutting materials, paints, adhesives, sealing materials, molding materials, etc. that can achieve high mechanical or physical strength, toughness, or high heat resistance. can provide industrial materials.

In the present application, solid powder is not simply a mixture of solid epoxy and solid curing agent, but rather a semi-cured state (B stage) that is obtained by mixing them and further reacting and curing them slightly. It is formed by pulverizing the

According to one composite material of the present invention, for example, when heat is applied, a solid powder segment typified by a solid powder resin and a liquid segment typified by a liquid resin are so to speak individually cured, thereby increasing toughness and The excellent functions of a solid epoxy resin having high impact resistance and the excellent functions of a liquid epoxy resin having adhesion to various materials and flexibility can be significantly exhibited.

In addition, according to one hard material of the present invention, by containing the inorganic particles and the above-described composite material, high adhesive strength, toughness, or high heat resistance that can withstand use in high-precision or high-load environments It is possible to provide paints, adhesives, sealing materials, molding materials, etc. that can realize the properties.

FIG. 5 is a schematic diagram showing a hard material in a second embodiment of the invention;

An example of a composite material, a hard material, and a method for producing a hard material, which are embodiments of the present invention, will be described in detail below.

<First embodiment>
The composite material of this embodiment comprises a solid powdery resin (A) containing a first epoxy resin (a1) and a first curing agent (a2), a second epoxy resin (b1) and a second curing agent (b2). It contains a liquid resin (B) containing.

1. About the solid powdery resin (A) The solid powdery resin (A) of the present embodiment is solid below 40°C, typically around room temperature (for example, about 25°C) or at 40°C. , and contains a first epoxy resin (a1) and a first curing agent (a2). In addition, the solid powdery resin (A) can contain additives such as catalysts and/or leveling agents. In addition, a more preferable solid powdery resin (A) is a resin that retains a solid shape when visually observed, and is typically solid even at a relatively high temperature of 30° C. or higher and 60° C. or lower. can retain its shape.

The type of the first epoxy resin (a1) is not particularly limited. Typical first epoxy resins (a1) are bisphenol A type, bisphenol F type, cresol novolac type, and/or hydroxyphenyl type, and the like. Also, the mass average molecular weight of the first epoxy resin (a1) is preferably 450 or more, more preferably 600 or more, still more preferably 800 or more. Moreover, if the first epoxy resin (a1) is bifunctional or higher, it can exhibit at least part of the effects of the present embodiment. From the viewpoint of exhibiting the effect of the present embodiment with higher accuracy, it is more preferable that the first epoxy resin (a1) is a tri- or higher functional resin. In addition, when both the weight average molecular weight of the first epoxy resin (a1) is within the above numerical range and the first epoxy resin (a1) is a tri- or higher functional resin, further This is a suitable example. In addition to the above, from the viewpoint of improving impact resistance, the first epoxy resin (a1) not only has a rigid structure, but also has a short chain (typically, 3 carbon atoms) that provides moderate flexibility. to the extent of ) is a more preferred embodiment.

Also, the type of the first curing agent (a2) is not particularly limited. Typical first curing agents (a2) are acid anhydride-based, imidazole-based, phenol-based, and/or dicyandiamide (also referred to as “DICY”)-based, and the like. From the viewpoint of increasing the heat resistance of the solid powder segment typified by the solid powder resin (A), it is a preferred embodiment that the activation temperature of the first curing agent (a2) is 100° C. or higher. Further, in order to further increase the adhesive strength and / or toughness of the composite material of the present embodiment, it is preferable that the solid powdery resin (A) is a highly crosslinkable resin, and that it has appropriate flexibility. More preferred.

As will be described later, the solid powdery resin (A) is obtained by premixing each raw material constituting the solid powdery resin (A), kneading the mixture, and then pulverizing and classifying the mixture. Here, the particle diameter/size of the powder of the solid powdery resin (A) is not particularly limited. It can be appropriately selected according to the application or workability of the composite material of the present embodiment. Also, when the solid powdery resin (A) is mixed with inorganic particles, an appropriate particle size/size can be selected according to the particle size/size of the inorganic particles. For example, in the present embodiment, it is a preferred aspect that the solid powdery resin (A) has a particle size/size approximately half that of the inorganic particles. In addition, when the composite material of the present embodiment is used for general cutting, grinding, or polishing applications, the solid powdery resin (A) preferably has an average particle size of 1 μm or more and 500 μm or less. A more preferable average particle size of the solid powdery resin (A) is 10 μm or more and 300 μm or less.

Here, with regard to the solid powdery resin (A), if the following condition (p) or (q) is satisfied, the property as a semi-cured state (B stage) in the "solid powdery" of the present invention is The present inventors have learned that expression can be performed with higher accuracy.
(p) The weight average molecular weight of the solid powdery resin (A) is 5,000 or less.
(q) The weight average molecular weight of the solid powdery resin (A) is at least twice the weight average molecular weight of the first epoxy resin (a1).

2. About the liquid resin (B) The liquid resin (B) of the present embodiment is liquid above 4°C, typically near room temperature (for example, about 25°C) or at 4°C, and is a second epoxy. It contains a resin (b1) and a second curing agent (b2). In addition, the liquid resin (B) may contain additives such as catalysts, thixotropic agents, pigments and/or leveling agents. A more suitable liquid resin (B) can maintain a liquid state even at a relatively low temperature of 4° C. or higher and 20° C. or lower.

In addition, since the liquid resin (B) of the present embodiment is mixed with the above-described solid powdery resin (A), from the viewpoint of improving workability in the mixing process and/or reducing manufacturing costs, the temperature is set at 15°C to 40°C The viscosity of the liquid resin (B) under the following conditions is preferably 10 mPa·s or more and 100 Pa·s or less.

Also, the type of the second epoxy resin (b1) is not particularly limited. Typical second epoxy resins (b1) are bisphenol A type, bisphenol F type, alicyclic, alkyl, and the like. Moreover, the mass average molecular weight of the second epoxy resin (b1) is preferably less than 800. In addition, from the viewpoint of improving workability or reducing manufacturing costs when a process such as coating, casting, and/or coating is performed by mixing with the solid powdery resin (A), the second epoxy resin (b1) It is a more preferable aspect that the weight average molecular weight of is less than 450. In addition, it is more preferable that the second epoxy resin (b1) is liquid in the temperature range of −20° C. or higher and 100° C. or lower from the viewpoint of improving the workability described above.

Also, the type of the second curing agent (b2) is not particularly limited. Typical second curing agents (b2) are amine-based and/or acid anhydride-based.

As described above, the composite material of this embodiment is formed by mixing the solid powdery resin (A) and the liquid resin (B). A known mixer/kneader can be used to manufacture the composite material of the present embodiment. Further, when the mixing step is performed, from the viewpoint of improving the workability and / or reducing the manufacturing cost, or from the viewpoint of dispersing as uniformly as possible, the temperature is set based on the preferred temperature ranges described above. Preferably, the processing speed and/or processing time is set as well as performed.

Moreover, in the mixing step described above, the existence ratio (mass ratio) of the solid powdery resin (A) and the liquid resin (B) is not particularly limited. The abundance ratio can be appropriately selected from the required balance of mechanical properties depending on the application of the composite material of this embodiment or the hard material of a second embodiment described later. From the viewpoint of increasing the adhesive strength, heat resistance, toughness, impact resistance, and/or flexibility of the composite material of this embodiment or the hard material of a second embodiment described later, solid powdery It is a preferred embodiment that the abundance ratio (mass ratio) of the resin (A) and the liquid resin (B) is in the range of A:B=9:1 to 1:9. In addition, from the viewpoint of further enhancing each of the technical characteristics described above, the existence ratio (mass ratio) of the solid powdery resin (A) and the liquid resin (B) is A:B = 1:9 to 7: A range of 3 is a further preferred aspect.

As described above, the composite material of the present embodiment can be realized as a composite material capable of solving at least one of the following technical problems (1) to (2).
(1) Realize high bonding strength to ceramics and the like.
(2) exhibit toughness, impact resistance, and/or flexibility even under rubbing and/or abrasive environments;

<Second embodiment>
FIG. 1 is a schematic diagram showing a hard material 100 of this embodiment. A hard material 100 of the present embodiment contains inorganic particles 30 and the composite material of the first embodiment. The composite material has a solid powder segment 10 typified by a solid powdery resin and a liquid segment 20 typified by a liquid resin.

The type of inorganic particles 30 is not particularly limited. Exemplary inorganic particles 30 include hard inorganic particles such as boron nitride, carbon silicide, aluminum nitride, carbon-based materials such as diamond, graphite, diamond-like carbon, carbon nanotubes, graphene, fullerenes, and/or alumina, silica, titania. ceramic particles such as Examples of the inorganic particles 30 described above may be of a single type, or may be used in combination of two or more types. From the viewpoint of preventing the strength of the hard material from decreasing due to the destruction of the inorganic particles themselves, it is a preferable aspect that the above-described hard inorganic particles and/or diamond are employed as the inorganic particles 30 .

The method for producing the hard material 100 of the present embodiment includes a mixing step of mixing the inorganic particles 30 and the composite material of the first embodiment to obtain a mixture, and a curing step of heating and curing the mixture. include.

First, a mixing step of mixing the inorganic particles 30 and the composite material of the first embodiment is performed. A known mixer/kneader can be used in this mixing step. Further, when the mixing step is performed, from the viewpoint of improving workability and / or reducing manufacturing costs, or from the viewpoint of dispersing as uniformly as possible, suitable each of the raw materials disclosed in the first embodiment Based on the temperature range, preferably the temperature is set and the processing speed and/or processing time are set.

Moreover, the existence ratio (mass ratio) between the inorganic particles 30 and the composite material of the first embodiment in the above-described mixing step is not particularly limited. The abundance ratio can be appropriately selected from the required balance of mechanical properties depending on the application of the hard material of the present embodiment. In addition, from the viewpoint of ensuring durability in use in severe friction/wear environments, etc., when the above-described hard inorganic particles are employed as the inorganic particles 30, the inorganic particles 30 and the composite material of the first embodiment A preferred example of the mixing ratio (mass ratio) of the inorganic particles 30 is 100 to about 10 to about 50 of the composite material.

After that, a curing step is performed in which the mixture in which the inorganic particles 30 and the composite material of the first embodiment are mixed is heated and cured. A known heating device can be used in this curing step. In addition, when the curing step is performed, it is preferable to set the temperature and/or the processing time from the viewpoint of sufficient curing while paying attention to the activation temperature of each curing agent used in the composite material.

[Example]
Examples and comparative examples are shown below to describe the present embodiment in more detail, but the examples are disclosed only for the purpose of illustrating the present embodiment and limit the present embodiment. not a thing In the examples, "parts" and "%" mean parts by mass and % by mass, respectively.

<Solid Powdery Resin (A) of the Present Example>
The powder raw materials of each component of the epoxy resin, curing agent, and additive shown in the first embodiment are mixed (dry blended) using a drum mixer (manufactured by Shinmaru Enterprises, model DX-200), and 100 C. for 1 minute to obtain a B-stage solid. After that, it is pulverized to several μm to about 150 μm using a pin mill pulverizer (manufactured by Yarya Machinery Co., Ltd., product name: Yarya type pulverizer), and a powder having an average particle size of 1 μm or more and 150 μm or less is obtained by an air classification method. By classifying, a solid powdery resin (A) is obtained.

<Liquid Resin (B) of the Present Example>
Liquid resin (B ).

<Composite material of the present embodiment>
The above solid powdery resin (A) and the above liquid resin (B) are mixed (or kneaded) at room temperature (about 25° C.) for 30 minutes in the above kneader mixer to obtain the composite material of this embodiment. obtain.

<Mixing step and curing step of inorganic particles and composite material of the present embodiment>
A mixture is obtained by mixing (or kneading) 50 parts of the composite material of this example with 100 parts of a mixture of silicon nitride and silicon carbide having an average particle size of 150 μm using the above kneader mixer. After that, the mixture is cast into a mold and then subjected to a curing step of applying pressure at 1000 kgF/cm ² and heating at 200° C. for 5 hours. As a result, a disk-shaped compact (hard material) having a diameter of 10 cm and a thickness of 5 mm is obtained.

<Performance evaluation>
The hard material described above was subjected to a three-point bending test, a tensile strength test, and further, by pressing against a 2-inch diameter silicon nitride single crystal wafer while rotating at a peripheral speed of 50 m / sec, the occurrence of chipping of the hard material. Adhesive strength, heat resistance, and impact resistance are evaluated from the presence or absence and the wear amount of the hard material. In addition, the hard material was simply rotated at rotational speeds of 80 m/s, 100 m/s, and 120 m/s to see if the hard material fractured. Material flexibility was evaluated.

[Example 1]
The components constituting the solid powdery resin (A) are 100 parts of JER-1004 (manufactured by Mitsubishi Chemical Corporation, molecular weight of about 1600), which is an example of the first epoxy resin (a1), and the first curing agent (a1). One example is 10 parts of DICY-based DICY #7 (manufactured by Mitsubishi Chemical Corporation, activation temperature of about 190° C.).
The components constituting the liquid resin (B) are 100 parts of JER-828 (manufactured by Mitsubishi Chemical Corporation, molecular weight of about 370), which is an example of the second epoxy resin (b1), and the second curing agent (b2). 5 parts of imidazole-based EMI-12 (manufactured by Shikoku Kasei Co., Ltd., activation temperature), which is an example, and 0.3 parts of Acronal 4F (manufactured by BASF) as an additive leveling agent. KS-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a defoaming agent is 0.3 parts.

The composite material of Example 1 was obtained by mixing the solid powdery resin (A) and the liquid resin (B) at a ratio of 1:1.

[Example 2]
The components constituting the solid powdery resin (A) are 100 parts of cresol novolac type epoxy resin N-690 (manufactured by DIC, molecular weight of 531 or more and about 1000), which is an example of the first epoxy resin (a1), 1 10 parts of DICY-based DICY#7 (manufactured by Mitsubishi Chemical Corporation, activation temperature of about 190° C.), which is an example of the curing agent (a1).
In addition, the components constituting the liquid resin (B) are 100 parts of JER-828 (manufactured by Mitsubishi Chemical Corporation, molecular weight of about 370), which is an example of the second epoxy resin (b1), and an example of the second curing agent (b2). 5 parts of imidazole-based EMI-12 (manufactured by Shikoku Kasei Co., Ltd., active temperature), 0.3 parts of Acronal 4F (manufactured by BASF) as an additive leveling agent, and an additive defoaming KS-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an agent is 0.3 parts.

The composite material of Example 2 was obtained by mixing the solid powdery resin (A) and the liquid resin (B) at a ratio of 1:1.

[Comparative Example 1]
Components constituting the liquid resin (B) are 100 parts of JER-828 (manufactured by Mitsubishi Chemical Corporation, molecular weight of about 370), which is an example of the second epoxy resin (b1), and an example of the second curing agent (b2). 5 parts of imidazole-based EMI-12 (manufactured by Shikoku Kasei Co., Ltd., active temperature), 0.3 parts of Acronal 4F (manufactured by BASF) as an additive leveling agent, and an additive antifoaming KS-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) as an agent is 0.3 parts. In addition, in Comparative Example 1, the solid powdery resin (A) was not used.

[Comparative Example 2]
The components constituting the solid powdery resin (A) are 100 parts of JER-1004 (manufactured by Mitsubishi Chemical Corporation, molecular weight of about 1600), which is an example of the first epoxy resin (a1), and an example of the first curing agent (a1). 10 parts of DICY-based DICY#7 (manufactured by Mitsubishi Chemical Corporation, activation temperature of about 190° C.). In Comparative Example 2, the liquid resin (B) was not used.

As a result of evaluating Examples 1 and 2 and Comparative Examples 1 and 2 for bending strength, tensile strength, adhesive strength, heat resistance, and impact resistance, the following results were obtained.
(1) The hard materials of Examples 1 and 2 exhibited significantly superior flexural strength to Comparative Examples 1 and 2 at room temperature (about 25°C) and in a heated environment.
(2) The hard materials of Examples 1 and 2 exhibited significantly superior tensile strength to Comparative Examples 1 or 2 at room temperature (about 25°C) and in a heated environment.
(3) The hard materials of Examples 1 and 2 had significantly less chipping, breakage, and wear than those of Comparative Examples 1 and 2, and exhibited significantly superior adhesive strength, heat resistance, and impact resistance.
(4) The hard materials associated with Examples 1 and 2 exhibited significantly better flexibility than Comparative Examples 1 or 2 without breaking at low rotational speeds.

As a result of supplementary confirmation investigations by the present inventors, the composite material obtained by mixing the solid powdery resin (A) and the liquid resin (B) at a ratio of 1:9, and the above-mentioned A composite material obtained by mixing the solid powdery resin (A) and the liquid resin (B) at a ratio of 7:3 can also exhibit technical effects equal to or greater than those of the composite material of Example 1 or 2. This knowledge was obtained.

Therefore, according to the composite material of this embodiment, it is possible to have excellent adhesive strength, toughness, impact resistance, heat resistance, and flexibility. In addition, a hard material comprising the composite material can exhibit the following effects (1) to (3).
(1) Exhibits high mechanical strength, especially at high temperatures.
(2) exhibit toughness, impact resistance, and/or flexibility even under rubbing and/or abrasive environments;
(3) Overall destruction can be suppressed or prevented by reducing the excessive load by appropriately falling off or the like.

The composite material of the present embodiment can be employed as a binder for a resin-bonded composite material that requires high mechanical properties, environmental resistance, and precision under severe friction/wear environments, for example. Typical examples where typical composite materials or hard materials are used include cutting (cutting materials), grinding or polishing members (abrasives), brakes and transmission pads for transportation equipment, and various sliding Although it is a part, it is also suitable as a paint, an adhesive, a sealant, a molding material, etc., and the application of the composite material or hard material of the present embodiment is not limited to the above examples.

Moreover, the disclosure of the above-described embodiments or examples is for the purpose of explaining the embodiments or examples, and is not intended to limit the present invention. In addition, variations that fall within the scope of the invention, including other combinations of the above-described embodiments or examples, are also intended to be covered by the claims.

The above-described embodiments and examples of composites and hard materials can be applied to a wide variety of applications as described above.

10 solid powder segment 20 liquid segment 30 inorganic particles 100 hard material

Claims (9)

a solid powdery resin (A) that is solid at 40° C. and contains a first epoxy resin (a1) and a first curing agent (a2);
a liquid resin (B) that is liquid at 4° C., containing the second epoxy resin (b1) and the second curing agent (b2) ;
The weight average molecular weight of the solid powdery resin (A) is 5000 or less, or twice or more the weight average molecular weight of the first epoxy resin (a1),
The existence ratio (mass ratio) of the solid powdery resin (A) and the liquid resin (B) is in the range of A:B = 9:1 to 1:9,
The solid powdery resin (A) and the liquid resin (B) are independent of each other,
Composites for binders . The weight average molecular weight of the first epoxy resin (a1) is 450 or more, and the first epoxy resin (a1) is bifunctional or more.
The composite material for a binder according to claim 1 . The weight average molecular weight of the second epoxy resin (b1) is less than 800, and the second epoxy resin (b1) is liquid in a temperature range of -20°C or higher and 100°C or lower.
The composite material for a binder according to claim 1 or 2 . The activation temperature of the first curing agent (a2) is 100° C. or higher.
The composite material for a binder according to any one of claims 1 to 3 . The average particle size of the solid powdery resin (A) is 1 μm or more and 500 μm or less.
The composite material for a binder according to any one of claims 1 to 4 . The viscosity of the liquid resin (B) under conditions of 15° C. or higher and 40° C. or lower is 10 mPa s or higher and 100 Pa s or lower.
The composite material for a binder according to any one of claims 1 to 5 . inorganic particles;
A composite material for a binder according to any one of claims 1 to 6 ,
hard material. wherein the hard material is an abrasive or cutting material;
A hard material according to claim 7 . A mixing step of mixing inorganic particles and the composite material for a binder according to any one of claims 1 to 6 to obtain a mixture;
a curing step of heating and curing the mixture;
A method of manufacturing hard materials.

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