KR20220065214A - Composite material with surface-treated plastic and anti-vibration rubber bonded and manufacturing method thereof - Google Patents

Abstract

The disclosed content relates to a composite material with surface-treated plastic and anti-vibration rubber bonded, which has excellent adhesion between a plastic layer and an adhesive layer by increasing the surface energy of the plastic layer; and a method for manufacturing the same. As one embodiment, suggested is a composite material with surface-treated plastic and anti-vibration rubber bonded, which comprises: a plastic layer composed of 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler; an adhesive layer formed on one surface of the plastic layer; and an anti-vibration rubber layer formed on one side of the adhesive layer.

Description

Composite material with surface-treated plastic and anti-vibration rubber bonded and manufacturing method thereof

The disclosed subject matter relates to a composite material in which a surface-treated plastic and vibration-proof rubber are adhered, which can be used for engine engine parts such as a cylinder head cover, a radiator tank, an oil pan, etc. of an automobile, and a manufacturing method thereof.

Unless otherwise indicated herein, the contents described in this identification are not prior art to the claims of this application, and the description in this identification is not admitted to be prior art.

Automotive parts, which were mainly manufactured from metal materials, are being manufactured from engineering plastics to reduce weight and reduce manufacturing costs. Engineering plastics are durable enough to replace metal and have excellent heat resistance, chemical resistance, and abrasion resistance. As an example of an automobile part using this, Korean Patent Application Laid-Open No. 10-2020-0082325 includes a base material including engineering plastic, and a filler added to the base material to improve wear resistance and lubricity, and the filler is surface modified. Disclosed is a wear-resistant lubricating composite material for automotive parts comprising a treated solid lubricant.

As another example, Korean Patent Laid-Open Publication No. 10-2019-0075486 discloses a plastic layer; and a steel plate laminated on one or both surfaces of the plastic layer, wherein the surface of the plastic layer laminated with the steel plate provides a composite material having a structure in which a polar functional group is introduced, and a method for manufacturing the same, wherein the composite material is an automobile Points that can be used as parts or structures are disclosed.

On the other hand, as engineering plastics are used, the cases of bonding plastics and other materials have increased, and accordingly, it is required to improve adhesion between different materials. In particular, when manufacturing a composite material comprising a plastic having a hydrophilic property and a rubber having a hydrophobic property, an adhesive capable of mediating them well is required because the properties of the plastic and the rubber are different from each other. In addition, it is necessary to properly treat the surface of the plastic to increase the adhesion between the plastic layer and the adhesive.

Patent Document 1: Republic of Korea Patent Publication No. 10-2020-0082325 (published on July 8, 2020) Patent Document 2: Republic of Korea Patent Publication No. 10-2019-0075486 (published on July 1, 2019)

The disclosed invention aims to provide a composite material having excellent adhesion between the plastic layer and the adhesive layer by increasing the surface energy of the plastic layer, and a method for manufacturing the same.

In addition, it is not limited to the technical problems as described above, and it is obvious that another technical problem may be derived from the following description.

The disclosed contents include a plastic layer comprising 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler; an adhesive layer formed on one surface of the plastic layer; and a surface-treated plastic including a vibration-proof rubber layer formed on one surface of the adhesive layer and a composite material to which the vibration-proof rubber is adhered as an embodiment.

According to the features of the disclosure, the composite material is a plastic layer preparation step consisting of 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler; a surface treatment step of increasing the surface energy of the plastic layer; an adhesive application step of applying an adhesive to one surface of the plastic layer after the surface treatment step; and a vibration-proof rubber layer forming step of adhering a vibration-proof rubber to the adhesive after the adhesive application step.

According to the composite material to which the surface-treated plastic and the anti-vibration rubber are adhered and the manufacturing method thereof according to an embodiment of the present disclosure, there is an advantage in that the surface energy of the plastic layer is increased, so that the adhesion between the plastic layer and the adhesive layer is excellent.

In addition, the adhesive strength between the adhesive layer and the anti-vibration rubber layer is excellent, so that it is possible to provide a composite material in which the plastic layer and the anti-vibration rubber layer are integrally formed.

In addition, when manufacturing automobile parts made of the disclosed composite material, it is possible to reduce the weight of the parts, and there is an advantage in that the durability of the parts is excellent.

Effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

1 is a flowchart of the disclosed composite material manufacturing method.
2 is a photograph illustrating a contact angle.
3 is a photograph comparing the surface of the plastic layer before and after the surface treatment step of the disclosed method for manufacturing a composite material.

Hereinafter, with reference to the accompanying drawings, the configuration and effects of preferred embodiments of the disclosed contents will be described. For reference, in the following drawings, each component is omitted or schematically illustrated for convenience and clarity, and the size of each component does not reflect the actual size. In addition, the same reference numerals refer to the same components throughout the specification, and reference numerals for the same components in individual drawings will be omitted.

The disclosed composite material to which the surface-treated plastic and the vibration-proof rubber are adhered includes a plastic layer, an adhesive layer, and a vibration-proof rubber layer.

The plastic layer serves to lighten the composite material and increase durability. Therefore, it is preferable that the plastic layer has a plastic resin having an engineering plastic component as a main component. The plastic layer contains a reinforcing agent and a filler together with a plastic resin.

The plastic resin corresponds to a main component constituting the plastic layer. Examples of the plastic resin material include polyamide, polyacetal, polycarbonate, polyethylene terephthalate, polypropylene, and the like. They have excellent strength and elasticity, as well as excellent impact resistance, abrasion resistance, heat resistance, and the like. Among them, nylon 6, nylon 66, polyethylene terephthalate and polypropylene are most preferable.

Nylon 6 and nylon 66 are the polyamide-based synthetic resins. Nylon 6 is produced by melt polymerization of caprolactam and adipic acid, and nylon 66 is produced by melt polymerization of hexamethylenediamine and adipic acid. am. Nylon 6 and nylon 66 both contain amide bonds, so they can form hydrogen bonds and thus absorb moisture. These properties may cause problems in that the disclosed composite material causes a volume change when exposed to moisture and reduces mechanical strength, so to improve these problems, a filler is added as follows.

The plastic resin material may be used by mixing the plastic resin materials. For example, nylon 66 and polyethylene terephthalate may be mixed in a ratio of 1:1 to 3:1. By mixing the two materials, the water absorption, which is the weakness of nylon 66, and the chemical resistance, which is the weakness of polyethylene terephthalate, can be supplemented. there is. As such, when two or more materials are mixed and used, it is preferable to use a compatibilizer as a filler. A compatibilizer refers to a substance that lowers the interfacial tension between two types of substances to prevent aggregation of only one substance. By adding a compatibilizer, different types of materials can be mixed evenly. Examples of the compatibilizer include an oxazoline-containing polymer and an epoxy-containing polymer.

The reinforcing agent serves to supplement the mechanical rigidity of the plastic layer. The reinforcing agent must have high tensile strength and elastic modulus, and excellent heat resistance and abrasion resistance. An example of a reinforcing agent is glass fiber. Glass fiber has the above properties, is easy to handle, and is economically reasonable, so it is most preferable as a material for a reinforcing agent.

The glass fibers may be in the form of a chopped strand or a yarn in which they are long connected. The shape of the glass fiber has a diameter of 10 μm to 12 μm, and a shape cut into small pieces with a length of 3 mm is most preferable. The glass fiber may be a glass fiber treated with a silane coupling agent in order to maximize the adhesion between the plastic layer and the adhesive layer.

The reinforcing agent is preferably contained in an amount of 30 to 35 parts by weight based on 60 parts by weight of the plastic resin. If the reinforcing agent is less than 30 parts by weight based on 60 parts by weight of the plastic resin, optimal strength and durability cannot be exhibited. Further, the adhesive force between the plastic layer and the adhesive layer cannot be maximally exhibited. On the other hand, when the reinforcing agent is more than 35 parts by weight based on 60 parts by weight of the plastic resin, components other than plastic among the components constituting the plastic layer increase, so that strength and impact resistance may be lowered.

The filler improves the tensile strength of the plastic layer and makes the plastic layer have an additional function, such as making the surface of the plastic layer uniform. Examples of the filler may include an adhesion improving agent, an impact resistance agent, a plasticizer, a flame retardant, an antistatic agent, a release agent, a compatibilizer, an antioxidant, a nucleating agent, and a colorant. In addition, if it is a material for adding the function of the plastic layer, it can be added.

The adhesion improving agent improves the adhesion between the plastic layer and the adhesive layer, and also serves to improve the adhesion between the adhesive layer and the anti-vibration rubber layer. It is preferable to basically include it as a filler. Graphene oxide and oxidized fine carbon fibers may be used as the adhesion improving agent. They have a functional group containing oxygen on the surface, and thus serve as a bridge between hydrophilicity and hydrophobicity, thereby increasing the adhesion between the plastic layer and the adhesive layer.

The impact resistance agent serves to impart impact resistance to the plastic layer. This allows the disclosed composite material to be utilized as an automobile part. Ethylene butyl acrylate copolymer, ethylene acrylate copolymer, ethylene-propylene copolymer and ethylene-octene copolymer may be used as the impact resistance agent.

The plasticizer serves to impart flexibility to the plastic layer. This allows the disclosed composite material to be molded into a curved shape. A polyester plasticizer or silicone oil may be used as the plasticizer.

The flame retardant serves to suppress or alleviate combustion of the plastic layer. As a flame retardant, a bromine flame retardant, a chlorine flame retardant, a phosphorus flame retardant, an inorganic flame retardant, etc. can be used. As the inorganic flame retardant, magnesium hydroxide, aluminum hydroxide, antimony oxide, and the like may be used.

The antistatic agent serves to suppress the generation of static electricity. Cationic antistatic agents, anionic antistatic agents, and nonionic antistatic agents can be used as antistatic agents, and among them, nonionic antistatic agents are most preferable.

The release agent serves to make it easy to take out of the mold when the disclosed composite material is molded, and the antioxidant prevents oxidation of the plastic layer so that the durability of the plastic layer can be maintained for a long time.

The filler is any one or more selected from the group consisting of an adhesion improving agent, an impact resistance agent, a plasticizer, a flame retardant, an antistatic agent, a mold release agent, a compatibilizer, an antioxidant, a nucleating agent, and a colorant, and it is preferable to add the necessary filler according to the use.

The filler preferably contains 3 to 10 parts by weight of the filler based on 60 parts by weight of the plastic resin. If the filler is less than 3 parts by weight based on 60 parts by weight of the plastic resin, there is a problem in that a function cannot be effectively added to the plastic layer. On the other hand, if the filler exceeds 10 parts by weight based on 60 parts by weight of the plastic resin, there may be a problem in that the basic properties of the plastic are lost.

An adhesive layer is formed on one surface of the plastic layer including the above components. The adhesive layer is characterized in that it is formed on one surface-treated surface of the cross-section of the plastic layer. By forming the adhesive layer on the surface-treated surface, the adhesive force between the plastic layer and the adhesive layer can be maximized.

The adhesive layer serves as a mediator between the plastic layer and the anti-vibration rubber layer. The adhesive layer is made of an adhesive. It is most preferable that the component of the adhesive has both the properties of a plastic layer having hydrophilic properties and a vibration-proof rubber layer having hydrophobic properties. Polyurethane-based, polyester-based, and polyolefin-based adhesives can be used as components of these adhesives.

In addition, an internal emulsifier or a surfactant may be added as an additive for improving the properties of the adhesive. In particular, when the adhesive layer is formed by adding a surfactant to the raw material of the adhesive, the adhesive layer can have both the properties of the plastic layer and the vibration-proof rubber layer, so that the adhesive force between the plastic layer and the vibration-proof rubber layer can be improved.

A vibration-proof rubber layer is formed on the other surface of the adhesive layer. The anti-rubber layer serves to absorb vibration and noise when the disclosed composite material is used as an automobile part.

As the anti-vibration rubber layer, acrylonitrile butadiene rubber, polychloroprene rubber, ethylene propylene diene rubber, silicone rubber, acrylic rubber, ethylene vinyl acetate rubber, urethane rubber, butyl rubber, natural rubber, styrene-butadiene rubber, etc. can be used. Among them, it is most preferable to use acrylonitrile butadiene rubber and polychloroprene rubber, which have excellent adhesion to the adhesive layer.

The disclosed composite material to which the surface-treated plastic and the anti-vibration rubber are adhered is manufactured through a manufacturing method including a plastic layer preparation step, a surface treatment step, an adhesive application step, and a vibration-proof rubber layer forming step, as shown in FIG. 1 .

The plastic layer preparation step (S1) refers to a step of manufacturing a plastic layer through the material of the plastic layer. In this step, 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler are extruded and melted and cooled to prepare a plastic layer.

After the plastic layer preparation step, a surface treatment step (S2) is performed.

The surface treatment step (S2) is a step of increasing the surface energy of the plastic layer, and corresponds to a process step for increasing the adhesion between the plastic layer and the adhesive layer.

In the surface treatment step according to the disclosed embodiment, ultraviolet rays are irradiated to the surface of the plastic layer. Specifically, the surface of the plastic layer is irradiated with ultraviolet rays having a wavelength of 200 nm to 350 nm for 30 seconds to 10 minutes. Through this, it is possible to increase the surface energy by modifying the surface structure of the plastic layer.

Usually, the wavelength of ultraviolet light refers to light in the range of 10 nm to 400 nm, and it is preferable to use ultraviolet light having a wavelength of 200 nm to 350 nm in the surface treatment step. If the UV wavelength is less than 200 nm, the energy of the UV light is relatively high, and there is a problem that the surface of the plastic layer may become more non-uniform than necessary. On the other hand, when the UV wavelength exceeds 350 nm, the energy is relatively low, so the surface of the plastic layer cannot be modified, and there may be a problem that the UV irradiation time is long.

It is preferable that the irradiation time of an ultraviolet-ray is 30 second - 10 minutes. If the UV irradiation time is less than 30 seconds, there is a problem in that the plastic layer cannot be sufficiently modified to increase the adhesion between the plastic layer and the adhesive layer. On the other hand, if the UV irradiation time exceeds 10 minutes, there is a problem that the surface of the plastic layer may become more non-uniform than necessary.

In the surface treatment step according to another disclosed embodiment, plasma treatment is performed on the surface of the plastic layer. Specifically, plasma treatment is performed for 5 seconds to 15 seconds under atmospheric pressure using oxygen, argon or nitrogen gas as an air flow. Through this, the surface energy of the plastic layer may be modified to increase the surface energy. In this case, the modification of the surface means that a functional group including oxygen may be formed on the surface of the plastic layer.

Plasma treatment does not require a vacuum device when it is performed under atmospheric pressure, so the process is simple and continuous treatment is possible.

The plasma treatment time is preferably 5 to 15 seconds. If the plasma treatment time is less than 5 seconds, there is a problem that the surface of the plastic layer is not sufficiently modified. On the other hand, if the plasma treatment time exceeds 15 seconds, functional groups containing oxygen are formed on the surface of the plastic layer more than necessary.

After the surface treatment step, it is characterized in that the contact angle of the surface of the plastic layer to water in the air is reduced by 10% to 20% compared to before the treatment.

As shown in FIG. 2 , the contact angle with respect to water in the air refers to an angle between the surface of the plastic layer and the surface of the water droplet when water droplets are dropped on the plastic layer. When the contact angle of the plastic layer to water in the air is large, it means that the surface energy of the plastic layer is small and the adhesive force between the adhesive and the plastic layer is small. Conversely, when the contact angle of the plastic layer to water in the air is small, it means that the surface energy of the plastic layer is large and the adhesive force between the adhesive and the plastic layer is large. Therefore, in order to increase the adhesive force between the plastic layer and the adhesive layer, the contact angle of the plastic layer with respect to water in the air should be small.

Finally, the bonding force between the plastic layer and the adhesive layer is strengthened through the surface treatment methods disclosed above. 3 is a photograph comparing the appearance when water droplets are dropped on the plastic layer before and after the surface treatment step. As shown in FIG. 3 , when water droplets are dropped on the plastic layer before surface treatment, the contact angle of the plastic layer with water in the air is large enough to show the interface of the water droplets, whereas after surface treatment, the interface of the water droplets disappears and the air of the plastic layer disappears. The contact angle for water is small.

After the surface treatment step, an adhesive application step (S3) of applying an adhesive to one surface of the plastic layer is performed. The adhesive is preferably applied to the surface-treated surface of the plastic layer. That is, it is preferable to apply the adhesive to the UV-treated or plasma-treated surface of the plastic layer.

As a method of applying the adhesive to the plastic layer in this step, there may be a method of spraying the adhesive through a nozzle device through which the adhesive is sprayed, a method of directly dipping the surface of the plastic layer into the adhesive, and the like.

After the adhesive application step, a vibration-proof rubber layer forming step (S4) of adhering a vibration-proof rubber to the adhesive is performed. The composite material disclosed through this step forms a vibration-proof rubber layer to finally have a function of absorbing noise and vibration.

The anti-vibration rubber layer is preferably formed by attaching the anti-vibration rubber to the surface to which the adhesive is applied.

The disclosed composite material is formed through the step of forming the anti-vibration rubber layer, and in order to utilize it as an automobile part, a process of molding the composite material is required.

Although preferred embodiments of the present invention have been described with reference to the accompanying drawings, the embodiments described in the present specification and the configurations shown in the drawings are only the most preferred embodiments of the present invention and represent all of the technical spirit of the present invention. Therefore, it should be understood that there may be various equivalents and modifications that can be substituted for them at the time of filing the present application. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all respects, and the scope of the present invention is indicated by the following claims rather than the detailed description, and the meaning and scope of the claims and their All changes or modifications derived from the concept of equivalents should be construed as being included in the scope of the present invention.

S1 plastic layer preparation step
S2 surface treatment step
S3 Adhesive application step
S4 Anti-vibration rubber layer formation step

Claims (7)

a plastic layer comprising 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler;
an adhesive layer formed on one surface of the plastic layer treated with ultraviolet light or plasma; and
A surface-treated plastic including a vibration-proof rubber layer formed on one surface of the adhesive layer and a composite material to which the vibration-proof rubber is adhered
The method according to claim 1,
The plastic resin is a composite material with a surface-treated plastic and vibration-proof rubber adhered, characterized in that at least one selected from the group consisting of nylon 6, nylon 66, polyethylene terephthalate and polypropylene
The method according to claim 1,
The filler is an adhesion improving agent, impact resistance agent, plasticizer, flame retardant, antistatic agent, mold release agent, compatibilizer, and a composite material having a surface-treated plastic and anti-vibration rubber adhesive, characterized in that at least one selected from the group consisting of anti-oxidants
A plastic layer preparation step comprising 60 parts by weight of a plastic resin, 30 to 35 parts by weight of a reinforcing agent, and 3 to 10 parts by weight of a filler;
a surface treatment step of increasing the surface energy of the plastic layer after the plastic layer preparation step;
an adhesive application step of applying an adhesive to the surface-treated surface of the plastic layer after the surface treatment step; and
After the adhesive application step, a vibration-proof rubber layer forming step of adhering a vibration-proof rubber to the adhesive.
5. The method according to claim 4,
The surface treatment step is a method of manufacturing a composite material to which a surface-treated plastic and a vibration-proof rubber are adhered, characterized in that the surface of the plastic layer is irradiated with ultraviolet rays having a wavelength of 200 nm to 350 nm for 30 seconds to 10 minutes.
5. The method according to claim 4,
The surface treatment step is a method of manufacturing a composite material having a surface-treated plastic and vibration-proof rubber adhered, characterized in that plasma treatment is performed for 5 seconds to 15 seconds under atmospheric pressure using oxygen, argon or nitrogen gas as an air stream
7. The method according to claim 5 or 6,
The surface of the plastic layer, which has undergone the surface treatment step, has a contact angle with respect to water in the air is reduced by 10% to 20% compared to that before the treatment.

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