JP2014201019A - Resin member containing aromatic polyether ketone resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin member containing an aromatic polyether ketone resin which can be produced easily and can improve bonding strength during bonding.SOLUTION: A resin member 1 comprises: a substrate part 2 composed of a resin material containing an aromatic polyether ketone resin as a main component; and a surface layer part 3 which is laminated on the substrate part 2 and in which an inorganic particles 5 having a hydrophilic property are mixed with a base resin layer 4 composed of the resin material, and is configured such that the inorganic particles 5 are exposed to a lower layer surface 3a which is a layer surface opposite to the substrate part 2 in the surface layer part 3.

Description

  The present invention relates to a resin member containing an aromatic polyether ketone resin.

In recent years, aromatic polyether ketone resins having high heat resistance and excellent chemical resistance have been used for various resin members. However, the aromatic polyetherketone resin has poor adhesion. Therefore, when it is necessary to assemble and fix the resin member by bonding the surface formed with the aromatic polyetherketone resin, the bonding target portion of the surface formed with the aromatic polyetherketone resin is selected. It is necessary to make it easy to adhere.
Examples of the easy adhesion means include a surface modification treatment that improves the hydrophilicity of the adhesion surface.
Further, as a technique other than the surface modification treatment for forming a hydrophilic surface, for example, Patent Document 1 discloses that “an organometallic compound having a hydrolyzable leaving group, an oligomer thereof and / or two or more kinds”. Describes a plastic molded article having a coating film of a hydrophilized paint containing a co-oligomer of the organometallic compound on at least one outermost layer of a plastic substrate.
As an example of the organometallic compound having a hydrolyzable leaving group of the hydrophilic paint, a fluorine-containing organometallic compound is described.
Moreover, polyether ether ketone resin is illustrated as a material of a plastic base material.

JP 2000-301054 A

However, the conventional technology for easily adhering a resin member having a surface portion of an aromatic polyetherketone resin as described above has the following problems.
The surface modification treatment requires a considerable amount of time for the treatment and also requires expensive treatment equipment, resulting in an increase in manufacturing cost. In addition, when only a part of the surface needs to be modified, there is a problem that the process becomes rather complicated.
In the technique described in Patent Document 1, although there is no specific evaluation in the examples, it is presumed that good adhesive strength can be obtained between the paint layer and the adhesive by applying the hydrophilic paint. . Moreover, since it is only necessary to apply a hydrophilic paint, it is considered that the production is easy.
However, since the paint layer of Patent Document 1 is formed by applying a highly hydrophilic paint to the surface of a hydrophobic plastic molded article, the adhesion strength of the paint layer to the surface of the plastic molded article is very strong. There is a problem that you can not.
In the first place, the invention described in Patent Document 1 has a hydrophilic surface for the purpose of improving easy cleaning, easy drainage, anti-fogging, anti-condensation, antistatic properties and biocompatibility of a wide variety of plastic molded products. The adhesion strength between the paint layer and the plastic molded product is such that it has abrasion resistance against wiping with a cotton cloth and contact with an aluminum plate. For this reason, even if good adhesive strength is obtained through the paint layer, the adhesion strength between the paint layer and the plastic molded product is weak, so the paint layer peels off from the surface of the plastic molded product together with the bonding partner member. As a result, the substantial adhesive strength may be reduced.
Moreover, since the hydrophilization paint of patent document 1 consists of an organometallic compound, it does not have heat resistance and chemical resistance like aromatic polyetherketone resin. For this reason, even if necessary adhesion strength is obtained, there is a problem that the heat resistance and chemical resistance may be deteriorated as a whole component.

  The present invention has been made in view of the problems as described above, and provides a resin member having an aromatic polyether ketone resin on the surface layer that is easy to manufacture and can improve the adhesive strength during bonding. The purpose is to do.

  In order to solve the above problems, a resin member containing the aromatic polyetherketone resin according to the first aspect of the present invention includes a base material portion made of a resin material mainly composed of an aromatic polyetherketone resin, A surface layer portion laminated on the base material portion and mixed with an inorganic material having hydrophilicity in the resin material, and the inorganic material is on the surface of the surface layer portion opposite to the base material portion. Suppose it is exposed.

  In the resin member containing the aromatic polyether ketone resin, the content of the inorganic material in the surface layer portion has a distribution that increases from the substrate portion side toward the layer surface side in the layer thickness direction. Is preferred.

  In the resin member containing the aromatic polyether ketone resin, it is preferable that the interface of the base material portion with the surface layer portion has an uneven shape.

  In the resin member containing the aromatic polyether ketone resin, the inorganic material is preferably made of a particulate inorganic material having a melting point higher than that of the aromatic polyether ketone resin.

  According to the resin member containing the aromatic polyether ketone resin of the present invention, the surface layer portion in which the inorganic material having hydrophilicity is mixed with the resin material is made of a resin material mainly composed of the aromatic polyether ketone resin. Since it is laminated | stacked on the base material part, there exists an effect that manufacture is easy and can improve the adhesive strength at the time of adhesion | attachment.

It is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyether ketone resin of the 1st Embodiment of this invention, and its A section enlarged view. It is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyetherketone resin of the 2nd Embodiment of this invention. It is a graph which shows distribution of the content rate of the inorganic material in the resin member containing the aromatic polyetherketone resin of the 2nd Embodiment of this invention. It is process explanatory drawing explaining an example of the manufacturing process of the resin member containing the aromatic polyether ketone resin of the 2nd Embodiment of this invention. It is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyetherketone resin of the modification (1st modification) of the 2nd Embodiment of this invention. It is a graph which shows distribution of the content rate of the inorganic material in the resin member containing the aromatic polyetherketone resin of the modification (1st modification) of the 2nd Embodiment of this invention. It is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyether ketone resin of the 3rd Embodiment of this invention, and the B section enlarged view.

  Embodiments of the present invention will be described below with reference to the accompanying drawings. In all the drawings, even if the embodiments are different, the same or corresponding members are denoted by the same reference numerals, and common description is omitted.

[First Embodiment]
The resin member containing the aromatic polyether ketone resin according to the first embodiment of the present invention will be described.
Fig.1 (a) is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyetherketone resin of the 1st Embodiment of this invention. FIG.1 (b) is the A section enlarged view in Fig.1 (a).

The resin member containing the aromatic polyetherketone resin of the present embodiment is a variety of parts that require characteristics such as heat resistance, chemical resistance, and high strength, which are the characteristics of the aromatic polyetherketone resin provided on the surface layer portion. Or part or all of the apparatus.
Therefore, the outer shape is not particularly limited as long as the configuration of the main part described later is provided. Moreover, the resin member which consists only of resin materials may be sufficient, for example, it consists of materials other than resin, such as another resin member, for example, metal, glass, etc. by insert, outsert, press-fit, welding, adhesion | attachment etc. It may be a resin member combined with the member.

Examples of components and devices that can use the resin member of the present embodiment include, for example, components of medical devices and medical instruments that require chemical resistance and heat resistance. These components may be for mechanical parts, such as an operation part of an endoscope, for example, and may be a female part of a treatment instrument, for example.
Examples of parts and devices in other fields include electric wire covering parts, bearings, housings and connectors in electronic parts, semiconductor CMP rings, aircraft door handles, and the like.
Below, the main part of a resin member is demonstrated as a structure of a member single-piece | unit.

  As shown in FIGS. 1 (a) and 1 (b), the resin member 1 (resin member containing an aromatic polyetherketone resin) of the present embodiment includes a base member 2 and a surface layer 3. With.

The base material portion 2 constitutes a surface layer portion along the outer shape of the resin member 1 and is made of a resin material having an aromatic polyether ketone resin as a main component. “Main component” means a component having the maximum content.
However, the base material part 2 may be formed only in the surface layer part which follows the external shape of the resin member 1, and may be formed to the deep layer part inside rather than including a surface layer part.
The specific shape of the base material portion 2 varies depending on the outer shape necessary for the resin member 1 and whether only the surface layer portion or the deep layer portion is formed. Since FIG. 1A is a schematic diagram, the upper surface 2a of the base material layer along the outer shape of the resin member 1 is drawn as a plane, but the shape of the upper surface 2a of the base material layer depends on the outer shape required for the resin member 1. Can be formed into an appropriate shape.
For example, when the resin member 1 is in the form of a sheet or plate, the base member 2 may be a sheet or plate member having substantially the same thickness as the resin member 1, or the base member 2 may be other The structure laminated | stacked on the surface of one or both of the thickness direction of the sheet-like or plate-shaped member by material may be sufficient.
Moreover, when the resin member 1 has a three-dimensional shape, the base material part 2 may comprise the shell-shaped layered body along the three-dimensional external shape of the resin member 1, or the base material part 2 is You may comprise the solid body along the three-dimensional external shape of the resin member 1. FIG.

Examples of the aromatic polyether ketone resin that is the main component of the base material 2 include polyether ether ketone (PEEK), polyether ketone (PEK), polyether ketone ketone (PEKK), and polyether ketone ester. Can be mentioned.
In the present embodiment, PEEK is adopted as an example. PEEK has a melting point of about 340 ° C. and a continuous use temperature of about 250 ° C., and is particularly excellent in heat resistance among thermoplastic resins.
Moreover, the aromatic polyether ketone resin is excellent in chemical resistance.
For example, as a medical instrument, it is necessary to withstand chemicals used for severe sterilization and heat resistance in use, but aromatic polyether ketone resins satisfy such chemical resistance and heat resistance conditions.
In addition to the aromatic polyetherketone resin, for example, alloy resins such as polyphenylsulfone and polybenzimidazole, and additives such as glass fillers and carbon fibers are added to the resin material used for the base material part 2 Is possible.

  Examples of the method for forming the base material portion 2 include molding with a resin material and machining of a resin material base material.

The surface layer portion 3 is a layered portion laminated on the base material layer upper surface 2a of the base material portion 2, and includes a base resin layer 4 and inorganic particles 5 (an inorganic material having hydrophilicity) mixed in the base resin layer 4. With.
The lower layer surface 3a of the surface layer portion 3 is in close contact with the base material layer upper surface 2a. For this reason, the base material layer upper surface 2 a of the base material part 2 constitutes an interface with the surface layer part 3.
The upper layer surface 3 b of the surface layer portion 3 is the surface of the resin member 1.
The surface layer portion 3 only needs to be formed on the surface of the portion that requires hydrophilicity in the resin member 1. The structure which covers only can be possible. However, when hydrophilicity does not become a problem in terms of function, the entire upper surface 2a of the base material layer may be covered.
The thickness of the surface layer portion 3 is not particularly limited as long as it can hold the inorganic particles 5 in such an amount that the necessary hydrophilicity can be obtained. However, when the surface layer portion 3 is used for bonding or printing, the thickness is set such that an adhesive strength necessary for holding the adherend or the printed layer under certain conditions is obtained.
Here, the necessary adhesive strength is a substantial adhesive strength required for maintaining adhesion, which is determined only by the bonding strength on the adhesive surface. Such substantial adhesive strength is, for example, the strength of the surface layer portion 3 itself so that the surface layer portion 3 is not broken or damaged when an external force is applied, or the surface layer portion 3 and the base material portion. 2 is also included.

  Examples of parts that require hydrophilicity include, for example, parts that are applied with an adhesive or pressure-sensitive adhesive to adhere to other members, parts that are printed or painted, and in use in areas rich in moisture such as in vivo. Examples include parts that require low friction, parts that want to suppress charging by promoting moisture adhesion, and parts that want to prevent the adhesion of dirt.

The base resin layer 4 is provided in order to stably hold the inorganic particles 5 on the base material layer upper surface 2a, and a resin material having excellent adhesion to the base material part 2 can be adopted. In order to obtain good adhesion, it is preferable that the compatibility between the resin material of the base resin layer 4 and the resin material of the base material portion 2 is good.
The adhesiveness with the base material part 2 is particularly good when the resin material of the base resin layer 4 is the same resin as the main component of the resin material constituting the base material part 2. However, since compatibility is good between aromatic polyetherketone resins, it is also possible to use a different kind of aromatic polyetherketone resin as the base resin layer 4 from the base material part 2.
Further, similar to the base material portion 2, various additives can be added to the base resin layer 4. However, in this case, the type and blending ratio of the additive in the base resin layer 4 may be different from the kind and blending ratio of the additive in the base material portion 2.
In the present embodiment, as an example, PEEK resin is employed for the base resin layer 4.

The inorganic particle 5 is a particle body made of an inorganic material having hydrophilicity. As such an inorganic material, a material having a large surface free energy is suitable, and the degree of hydrophilicity can be evaluated by, for example, the contact angle of water.
As the hydrophilicity of the inorganic material used for the inorganic particles 5, the water contact angle is preferably 0 ° or more and 50 ° or less, and more preferably 0 ° or more and 25 ° or less.
Examples of preferable inorganic materials for the inorganic particles 5 include SiO ₂ (silica), TiO _{2 and the} like.

In the present embodiment, the inorganic particles 5 are mixed so as to be dispersed substantially uniformly in the base resin layer 4, and as shown in FIG. 1B, a part of the inorganic particles 5 is present on the upper layer surface 3b. Partially exposed. Therefore, when the content of the inorganic particles 5 is C (wt%) (where 0 <C <100), the inorganic particles occupy the total area of the surface layer portion 3 in consideration of the density of the inorganic particles 5. 5 exposure amount can be calculated.
Since the hydrophilicity as the surface layer portion 3 is determined by the ratio of the exposure amount of the base resin layer 4 and the exposure amount of the inorganic particles 5, in order to improve the hydrophilicity, the exposure amount of the inorganic particles 5 is increased. The content of the inorganic particles 5 may be increased.
On the other hand, when the content of the inorganic particles 5 is increased, the range of the inorganic particles 5 in contact with the upper surface 2a of the base material layer is also increased, so that the bonding strength with the base material portion 2 is decreased.
Therefore, the content of the inorganic particles 5 is preferably set so that the balance between the bonding strength between the base material portion 2 and the surface layer portion 3 and the hydrophilicity of the surface of the surface layer portion 3 is good.

The average particle diameter of the inorganic particles 5 is preferably 0.001 μm or more and 1 μm or less, and more preferably 0.01 μm or more and 0.1 μm or less.
Regarding the particle diameter of the inorganic particles 5, the smaller the particle diameter, the easier it is to improve the content. Moreover, if it is the same content rate, compared with the case where a particle size is larger, the surface area of the inorganic particle 5 exposed from the upper layer surface 3b can be increased more.
On the other hand, if the particle size of the inorganic particles 5 is increased, the average protrusion amount of the inorganic particles 5 from the upper layer surface 3b can be increased.

  As a suitable specific example of the inorganic particles 5 in the present embodiment, for example, a configuration in which silica particles having an average particle diameter of 1 μm are mixed with the base resin layer 4 at a content rate of 50 wt% can be given.

In order to manufacture the resin member 1 having such a configuration, for example, the shape of the base material portion 2 is formed by injection molding or the like.
Next, the surface layer part 3 is formed in the site | part which should form the surface layer part 3 on the base material layer upper surface 2a of the base material part 2 by the thermal spray method etc.
For example, the surface layer portion 3 is formed by spray-coating with a spray gun a heated melt in which a resin material to be the base resin layer 4 and inorganic particles 5 are mixed.
For example, when the base resin layer 4 which is a specific example of the present embodiment is PEEK and the inorganic particles 5 are silica particles, the heating temperature for forming the heated melt is preferably about 380 ° C.
When the heat-dissolved material is applied to the base material layer upper surface 2a, a part of the resin material on the base material layer upper surface 2a is dissolved or softened, and is in close contact with the resin material in the heat-dissolved material. Solidify with. Thereby, the interface of resin materials adheres firmly mutually.
In this way, the resin member 1 is manufactured.

According to the resin member 1 having such a configuration, the surface layer portion 3 is firmly adhered to the base material portion 2, and hydrophilic inorganic particles 5 are present on the upper layer surface 3 b of the surface layer portion 3. It is exposed at an occupied area ratio corresponding to the content ratio of the inorganic particles 5.
For this reason, the hydrophilicity as the whole surface of the surface layer part 3 can be improved by setting the occupation area rate of the inorganic particle 5 appropriately.
Thereby, for example, when an adhesive is applied on the upper layer surface 3b, even if the adhesive has poor adhesiveness with the base resin layer 4, it is between the inorganic particles 5 exposed on the upper layer surface 3b. An adhesive part is formed. As a result, an adhesive strength corresponding to the occupied area ratio of the inorganic particles 5 is obtained.
Further, since the surface layer portion 3 is obtained by solidifying the heat-dissolved material of the resin material of the base resin layer 4 and the inorganic particles 5, the inorganic particles 5 can be firmly held.
Moreover, since the surface layer part 3 contains the base resin layer 4 which consists of the same kind of resin material with favorable compatibility with the base material part 2, adhesiveness with the base material layer upper surface 2a is good.
For this reason, for example, when another member is bonded onto the surface layer portion 3, even when an external force is applied to peel off the other member, the area occupied by the base resin layer 4 on the lower layer surface 3 a is determined. Since it has adhesiveness, it can improve adhesive strength compared with the case where different materials with poor compatibility are in close contact with each other.

Further, in the resin member 1, by forming the surface layer portion 3, it is possible to impart hydrophilicity only to a portion that requires hydrophilicity.
The surface layer portion 3 can be easily formed even in an air atmosphere by, for example, spray coating using a thermal spray method. Therefore, the surface layer portion 3 can be manufactured in comparison with a case where hydrophilicity is imparted by surface modification processing that requires expensive processing equipment. It becomes easy. In addition, the manufacturing cost can be reduced.

[Second Embodiment]
Next, the resin member containing the aromatic polyether ketone resin of the 2nd Embodiment of this invention is demonstrated.
FIG. 2 is a schematic cross-sectional view showing the configuration of the main part of a resin member containing an aromatic polyether ketone resin according to the second embodiment of the present invention. FIG. 3 is a graph showing the distribution of the content of the inorganic material in the resin member containing the aromatic polyether ketone resin according to the second embodiment of the present invention. The horizontal axis of the graph is the position in the layer thickness direction, and the vertical axis is the content (wt%) of the inorganic particles 5 that are inorganic materials.

  As shown in FIG. 2, the resin member 11 (resin member containing an aromatic polyetherketone resin) of this embodiment is replaced with a surface layer portion in place of the surface layer portion 3 of the resin member 1 of the first embodiment. 13 is provided. Hereinafter, a description will be given centering on differences from the first embodiment.

The surface layer portion 13 is a multilayered layer having a thickness h sandwiched between a lower layer surface 13a in close contact with the substrate layer upper surface 2a of the substrate portion 2 and an upper layer surface 13b forming the surface of the resin member 11. Part.
The number of layers of the surface layer portion 13 is not particularly limited as long as it is two or more. In the present embodiment, as an example, the lowermost layer 13A, the first intermediate layer 13B, the second intermediate layer 13C, the third intermediate layer 13D, Six layers including the 4 intermediate layer 13E and the uppermost layer 13F have a layer structure in which the lower layer surface 13a is laminated in this order. Hereinafter, when these six layers are collectively referred to as each layer of the surface layer portion 13.
Each layer of the surface layer portion 13 is formed by mixing the resin material constituting the base resin layer 4 of the first embodiment and the inorganic particles 5 at different blending ratios.
The graph shown in FIG. 3 shows an example of the distribution of the content of the inorganic particles 5 in the surface layer portion 13 in the layer thickness direction.

The lowermost layer 13A is a layered portion in which the content of the inorganic particles 5 is 0 wt%, and is composed of only the resin material constituting the base resin layer 4. The resin material: inorganic particle 5 blending ratio (hereinafter simply referred to as blending ratio). ) Is 100: 0. The thickness of the bottom layer 13A is _{h A.}
The first intermediate layer 13B is a layered portion in which the content of the inorganic particles 5 is C _B wt% (however, 0 <C _B <100) [blending ratio (100−C _B ): C _B ], and the layer thickness is h _B.
The second intermediate layer 13 </ _b > C is a layered portion in which the content of the inorganic particles 5 is C _C wt% (where C _B <C _C <100) [mixing ratio (100−C _C ): C _C ], and the layer thickness is it is a _{h C.}
The third intermediate layer 13D is a layered portion in which the content of the inorganic particles 5 is C _D wt% (where C _C <C _D <100) [compounding ratio (100−C _D ): C _D ], and the layer thickness is it is a _{h D.}
The fourth intermediate layer 13E is a layered portion in which the content of the inorganic particles 5 is C _E wt% (where C _D <C _E <100) [compounding ratio (100−C _E ): C _E ], and the layer thickness is it is _{h E.}
The uppermost layer 13F is a layered portion in which the content of the inorganic particles 5 is C _F wt% (where C _E <C _F <100) [compounding ratio (100−C _F ): C _F ]), and the layer thickness is h. _F.
Here, the layer thicknesses h _A , h _B , h _C , h _D , h _E , h _F are all greater than 0 and less than h, and the sum of these is h.

With such a layer configuration, the surface layer portion 13 has a distribution in which the content of the inorganic particles 5 within the layer thickness h changes stepwise in five steps between 0 wt% and 100% (FIG. 3 line 100).
The layer thickness of each layer of the surface layer portion 13 and the content of the inorganic particles 5 in each intermediate layer can be set to appropriate numerical values as necessary. In FIG. 3, as an example, the layer thickness of each layer of the surface layer portion 13 is equal, and the content ratios C _B , C _C , C _D , C _E , and C _F are 20%, 40%, 60%, and 80%, respectively. , 90%, and so on.

The resin member 11 having such a configuration can be manufactured in substantially the same manner as in the first embodiment.
4A and 4B are process explanatory views illustrating an example of a manufacturing process of a resin member including an aromatic polyetherketone resin according to the second embodiment of the present invention.

First, the shape of the base material portion 2 is formed by, for example, injection molding.
Next, each layer of the surface layer portion 13 is sequentially formed at a portion where the surface layer portion 13 on the upper surface 2a of the substrate portion 2 is to be formed by a thermal spray method or the like.
For example, as shown in FIG. 4 (a), a heat melt M _A resin material comprising a base resin layer 4 was spray applied by a spray gun 14 to form a bottom layer 13A.
The heating temperature for forming the heated melt M _A, when the resin material is PEEK, is preferable about 380 ° C. (hereinafter same).
Heating melt M _A is, when applied to a substrate layer upper surface 2a, a part of the resin material of the substrate layer top surface 2a is dissolved or softened in close contact with the heated melt M _A, the heat radiation in this state Proceeds and solidifies. Thereby, the interface of resin materials adheres firmly mutually.

Next, as shown in FIG. 4 (b), a resin material and inorganic particles 5, the compounding ratio _(100-C B): the heating lysates _{M B} of the mixture obtained by mixing _{C B,} the spray gun 14 top The first intermediate layer 13B is formed by spray coating on the lower layer 13A.
As described above, the spray coating is repeated while changing the blending ratio of the heated melt, thereby forming the second intermediate layer 13C, the third intermediate layer 13D, the fourth intermediate layer 13E, and the uppermost layer 13F in this order.
In this way, the resin member 11 is manufactured.

According to the resin member 11 having such a configuration, the lower layer surface 13a of the surface layer portion 13 is formed by the surface of the lowermost layer 13A whose resin material is 100 wt%, and the upper layer surface 13b of the surface layer portion 13 is The inorganic particles 5 are formed by the surface of the uppermost layer 13F having a C _F content (where C _F is less than 100 wt%).
For this reason, compared with the said 1st Embodiment, while the lowermost layer 13A closely_contact | adheres to the base material part 2, the hydrophilic property of the uppermost layer 13F is improved.
Further, the lowermost layer 13A and the uppermost layer 13F include a first intermediate layer 13B, a second intermediate layer 13C, a third intermediate layer 13D, and a fourth intermediate layer 13E in which the content of the inorganic particles 5 increases stepwise. Therefore, the change in the composition ratio of the constituent components at each interface is reduced, and the discontinuity at the interface is alleviated. For this reason, the bias | inclination of the adhesive strength in the surface layer part 13 is reduced, and it becomes difficult for only a specific interface to become weak.
For this reason, the intensity | strength at the time of receiving external force can be improved. For example, when another member is bonded to the surface layer portion 13, the stress that causes peeling failure is dispersed between the base material portion 2 and the surface layer portion 13 and at each interface in the surface layer portion 13. For this reason, the strength of the surface layer portion 13 itself is increased, and when the surface layer portion 13 is adhered, the substantial adhesive strength can be improved.

[First Modification]
Next, the resin member containing the aromatic polyetherketone resin of the modified example (first modified example) of the present embodiment will be described.
FIG. 5: is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyetherketone resin of the modification (1st modification) of the 2nd Embodiment of this invention. FIG. 6 is a graph showing the distribution of the content ratio of the inorganic material in the resin member including the aromatic polyetherketone resin according to the modified example (first modified example) of the second embodiment of the present invention. The horizontal axis of the graph is the position in the layer thickness direction, and the vertical axis is the content (wt%) of the inorganic particles 5 that are inorganic materials.

  As shown in FIG. 5, the resin member 21 (resin member containing an aromatic polyether ketone resin) of the present modification is replaced with a surface layer portion in place of the surface layer portion 13 of the resin member 11 of the second embodiment. 23. Hereinafter, a description will be given focusing on differences from the second embodiment.

The surface layer portion 23 has a thickness h sandwiched between a lower layer surface 23a in close contact with the base material layer upper surface 2a of the base material portion 2 and an upper layer surface 23b forming the surface of the resin member 21, It is formed as an inclined layer in which the composition ratio between the resin material constituting the base resin layer 4 of the first embodiment and the inorganic particles 5 changes smoothly in the layer thickness direction.
That is, if the specific position in the layer thickness direction is x (where 0 ≦ x ≦ h) and the content of the inorganic particles 5 is expressed as C (x), the function C (x) is C (0) = 0. (Wt%), C (h) = _Cmax (wt%) (where 0 < _Cmax <100), and expressed as a monotonically increasing function in a broad sense in which the derivative is continuous in the interval of 0 <x <h. Is done. Moreover, the content rate of the resin material is represented by 100-C (x).
Since FIG. 5 is a schematic diagram, the density of the halftone dots of the surface layer portion 23 is changed stepwise for convenience of illustration, but the density of the halftone dots shown in the figure is irrelevant to the change of the function C (x). is there.

In FIG. 4, the example of distribution in the layer thickness direction of the content rate of the inorganic particle 5 in the surface layer part 23 is shown.
The straight line 101 is a straight line connecting between C (0) = 0 (wt%) and C (h) = C _max (wt%), and the content C (x) increases in proportion to x. An example is shown.
A curve 102 is an arcuate curve that curves between C (0) = 0 (wt%) and C (h) = C _max (wt%), and the content C (x) is x = An example in the case of a monotonically increasing function in a narrow sense in which the rate of increase increases sharply in the vicinity of 0 and gradually decreases as x = h is shown.
A curve 103 is an arcuate curve that curves between C (0) = 0 (wt%) and C (h) = C _max (wt%), and the content C (x) is x An example in the case of a monotonically increasing function in a narrow sense in which the rate of increase gradually increases in the vicinity of = 0 and gradually increases toward x = h is shown.
A curve 104 is a curve that connects C (0) = 0 (wt%) and C (h) = C _max (wt%) in a generally inverted S shape as a whole, and is an arcuate curve that curves upward. A horizontal straight line and an arcuate curve that curves downward are sequentially joined. That is, the change in the content rate C (x) increases sharply in the vicinity of x = 0, then the increase rate gradually decreases to a constant value, and further increases gradually toward x = h and then gradually increases. This represents an example of a monotonically increasing function in a broad sense where the rate is increased.

  The resin member 21 having such a configuration is the same as that of the second embodiment except that the layer formation is performed by continuously changing the blending ratio of the resin material and the inorganic particles 5 in the heated melt. Can be manufactured.

In the resin member 21 of the present modification, the surface layer portion 23 smoothly increases from 0 wt% to C _max (wt%) in the content rate C (x) of the inorganic particles 5 (including the case where a constant value is maintained in part). ) It is formed as an inclined layer. For this reason, the base material part 2 and the surface layer part 23 are laminated | stacked, without having an interface based on the difference in composition ratio.
For this reason, since the weak interface with respect to an external force is not formed in the layer thickness direction, the substantial adhesive strength can be further improved as compared with the second embodiment.

[Third Embodiment]
Next, the resin member containing the aromatic polyether ketone resin of the 3rd Embodiment of this invention is demonstrated.
Fig.7 (a) is typical sectional drawing which shows the structure of the principal part of the resin member containing the aromatic polyetherketone resin of the 3rd Embodiment of this invention. FIG.7 (b) is the B section enlarged view in Fig.7 (a).

  As shown in FIG. 7A, the resin member 31 (resin member containing an aromatic polyetherketone resin) of the present embodiment includes a base material portion 2 and a surface layer portion of the resin member 1 of the first embodiment. In place of 3, a base material portion 32 and a surface layer portion 33 are provided. Hereinafter, a description will be given centering on differences from the first embodiment.

The base material portion 22 includes a base material layer upper surface 22a made of a rough surface having an uneven shape, instead of the base material layer upper surface 2a of the base material portion 2 of the first embodiment.
The uneven shape on the upper surface 22a of the base material layer is for improving the adhesion with the surface layer portion 33. For example, an uneven shape having a surface roughness Ra (μm) of 0.01 to 0.9 is suitable. It is.
Such a concavo-convex shape of the upper surface 22a of the base material layer is formed, for example, by forming the molding surface of the molding die into a concavo-convex shape when the base material portion 2 is molded, and transferring the concavo-convex shape of the molding surface. Can do.
In addition, as another forming method, after forming the base material layer upper surface 22a as a smooth surface, for example, rough surface processing such as sandblasting can be performed.

  The surface layer portion 33 is formed by laminating the same structure as the surface layer portion 3 of the first embodiment on the base material layer upper surface 22a of the base material portion 32, and instead of the lower layer surface 3a, Only the surface layer portion 3 is different from the surface layer portion 3 only in that it includes a lower layer surface 33a closely adhered along the uneven shape of the upper surface 22a of the base material layer.

  Such a resin member 31 can be manufactured in the same manner as the resin member 1 of the first embodiment except that the base layer upper surface 32a is formed as a rough surface.

According to the resin member 31 of the present embodiment, the surface layer portion 33 is formed in close contact with the roughened base material layer upper surface 32a, so that the base material layer upper surface 32a is made of a smooth surface. Thus, the bonding strength between the base material portion 22 and the surface layer portion 33 can be improved.
For this reason, for example, when another member is bonded to the surface layer portion 33, peeling between the base material portion 32 and the surface layer portion 33 hardly occurs, so that the adhesive strength can be improved.

In the above description of each embodiment and the first modification, the configuration of the main part of the resin member as a single member is described. For this reason, for example, in the resin member 1, the inorganic particles 5 have been described as being exposed from the upper layer surface 3 b and also from the outer surface of the resin member 1.
However, since the inorganic particles 5 impart hydrophilicity to the surface of the surface layer portion 3, the inorganic particles 5 need only be exposed from the upper layer surface 3 b, and are exposed on the outer surface of the portion that does not require hydrophilicity of the resin member 1. It is not essential to be. For example, the resin member 1 can be an assembly bonded to another member in the surface layer portion 3 by utilizing the hydrophilicity of the surface layer portion 3, and in this case, the resin member 1 is exposed from the upper layer surface 3b. The inorganic particles 5 are covered with an adhesive layer or a pressure-sensitive adhesive layer so that they are not exposed from the outer surface as an assembly.

In the description of each of the embodiments and the first modification, the example in which the surface layer portion is formed by the thermal spray method has been described. However, the method for forming the surface layer portion is not limited thereto.
For example, a forming method for electrostatic coating, a forming method for powder coating, or the like can be used.

  In the description of the second and third embodiments, the surface layer portions 13 and 23 have been described using an example in which the content of the inorganic particles 5 in the layered portion in contact with the base layer upper surface 2a is 0 wt%. , 0 wt% is not essential. For example, as in the case of the first embodiment, the content of the inorganic particles 5 may be higher than 0 wt% if the adhesive strength with respect to the base material portion 2 is satisfied.

  Further, in the description of each of the above embodiments and the first modification, an example in which the inorganic material having hydrophilicity is the inorganic particle 5 has been described. However, the inorganic material is not limited to a particulate form, and may be an irregular powder form in which the particle diameter cannot be defined, or may have a shape such as a piece, a rod, a needle, or a thread. Good.

  Further, all the components described above can be implemented by being appropriately combined or deleted within the scope of the technical idea of the present invention.

Below, the specific Example of the said embodiment is demonstrated with a comparative example.
Table 1 below summarizes the manufacturing conditions and evaluation results of the examples and comparative examples.

[Example 1]
Example 1 is an example corresponding to the first embodiment.
That is, the resin material of the base material part 2 is Victrex (registered trademark) PEEK-90G (trade name; manufactured by Victrex) whose main component is PEEK resin. The surface state of the base material layer upper surface 2a is a smooth surface by molding.
The outer shape of the base member 2 was a flat test piece shape.
The base resin layer 4 of the surface layer portion 3 is formed by dissolving VICOTE (registered trademark) powder 804B1K (trade name; manufactured by Victorex) mainly composed of PEEK resin.
The inorganic particles 5 in the surface layer portion 3 are silica particles having an average particle diameter of 0.1 μm.
The compounding ratio of the base resin layer 4 and the inorganic particles 5 was 50:50.
In such a resin member 1 of Example 1, the base material portion 2 is formed by molding, and VICOTE (registered trademark) powder 804B1K and silica particles are heated on the entire surface of the base material layer upper surface 2a at a blending ratio of 50:50. The melt was sprayed with a spray gun and sprayed by a thermal spray method. Thereby, the surface layer portion 3 having a layer thickness of 10 μm was formed on the upper surface 2a of the base material layer.
The heating temperature of the heated melt was 380 ° C. The time required for spraying was 1 minute.

[Example 2]
Example 2 is another example corresponding to the first embodiment, and the only difference is that in Example 1, the inorganic particles 5 are replaced with TiO ₂ having an average particle diameter of 0.1 μm.

[Example 3]
Example 3 is an example corresponding to the second embodiment described above, and a surface layer part 13 is formed instead of the surface layer part 3 of Example 1.
The base resin layer 4 and the inorganic particles 5 are the same as in Example 1, and the lowermost layer 13A, the first intermediate layer 13B, the second intermediate layer 13C, the third intermediate layer 13D, and the fourth intermediate layer 13E of the surface layer portion 13 are used. The contents of silica particles in the uppermost layer 13F are 0%, 20%, 40%, 60%, 80%, and 90%, respectively. Each layer thickness is 10 μm in common.
For this reason, the average content of the inorganic particles 5 in the surface layer portion 13 is 50 μm.
In such a resin member 31 of Example 3, the base material portion 2 is formed by molding, and the compounding ratio of VICOTE (registered trademark) powder 804B1K and silica particles is 100: 0 on the entire surface of the upper surface 2a of the base material layer. , 20:80,..., 90:10, and formed by sequentially spraying with a spray gun using a heated melt. As in Example 1, the heating temperature of the heated melt was 380 ° C. The time required for spraying was 10 seconds for each layer.

[Example 4]
Example 4 is another example corresponding to the second embodiment, and the only difference is that the inorganic particles 5 are made of TiO ₂ in Example 3.

[Example 5]
Example 5 is an example corresponding to the third embodiment, and instead of the base material part 2 and the surface layer part 3 of Example 1, a base material part 32 and a surface layer part 33 are formed. is there.
After the base material part 32 was formed in the same manner as in Example 1, the base material part 32 was subjected to sand blasting to form the base material layer upper surface 32a.
The sand blast treatment was performed using gravity suction type air blast MY-40 (trade name; manufactured by Shinto Brater Co., Ltd.). The grinding powder used was a particle size F220 of Sacrandom (registered trademark) (trade name; manufactured by Nippon Grinding Abrasive Co., Ltd.), which is an alumina abrasive, and the treatment time was 1 minute.
Thereby, the surface roughness Ra of the surface roughness Ra (micrometer) of 0.1 was formed for the surface roughness of the base material layer upper surface 32a.
The surface layer portion 33 was formed in the same manner as the surface layer portion 3 of Example 1 except that the surface layer portion 33 was formed on the roughened base material layer upper surface 32a.

[Comparative Examples 1 and 2]
Comparative Example 1 is the base material part 2 itself, and corresponds to a configuration in which the surface layer part 3 is removed in Example 1.
In Comparative Example 2, TiO ₂ having an average particle diameter of 0.1 μm is vacuum-deposited on the upper surface 2a of the base material portion 2 to form a layered portion having a layer thickness of 10 μm.
Therefore, in Comparative Example 2, the lowermost layer 13A, the first intermediate layer 13B, the second intermediate layer 13C, the third intermediate layer 13D, and the fourth intermediate layer 13E in Example 4 are removed, and only the uppermost layer 13F is formed. It corresponds to the case.

[Evaluation]
As evaluation of these Examples 1-5 and Comparative Examples 1 and 2, contact angle measurement, peeling evaluation, and adhesive strength measurement were performed.
The contact angle measurement was performed by SCA20 of Datephysics, Inc., and the contact angle of water on the surface of the surface layer portion of each resin member (in the case of a comparative example, the surface of the base material layer upper surface 2a and the TiO ₂ layer; the same applies hereinafter)
The peel evaluation was performed by performing a peel test at 50 squares according to the cross cut test method of JIS K5400 and evaluating the peel number. The peel number of 0/50 was “◯ (good)”, and the peel number of 1/50 or more was “x (no good)”.
In the measurement of the adhesive strength, an epoxy adhesive was applied to the surface of each resin member on which the surface layer portion was formed, and a stainless steel plate having a thickness of 2 mm was adhered to form a test sample. And according to JISK6850, the adhesive strength was measured by measuring the load which an adhesion part fracture | ruptures with a tensile shear tester.

In the contact angle measurement, as shown in Table 1, Examples 1 to 5 were 15 °, 17 °, 10 °, 11 °, 10 °, Comparative Example 1 was 71 °, and Comparative Example 2 was 16 °, respectively. there were.
That is, it turns out that Examples 1-5 which provided the surface layer part and Comparative Example 2 which provided the TiO2 layer on the surface became 10 degrees-17 degrees, and favorable hydrophilicity was provided. The difference between the inorganic particles 5 being silica particles or TiO ₂ particles is as small as 1 ° to 2 °, and the difference depending on the content is larger.
That is, when the silica particles or TiO ₂ particles are 100% distributed on the surface of the layer, the contact angle is the smallest. Compared with the result of Comparative Example 1, the contact angle of PEEK alone is 71 °, the content rate Even 50% is a much better result.

  In the peeling evaluation, no peeling was observed in any of Examples 1 to 5, and it was determined as “◯”, whereas in Comparative Example 2, 20% was peeled off, and thus “x” was determined.

The adhesive strengths of Examples 1 to 5 were measured as 23 MPa, 25 MPa, 29 MPa, 28 MPa, and 31 MPa, and Comparative Examples 1 and 2 were measured as 5 MPa and 12 MPa, respectively.
Comparing the examples, the best adhesive strength was obtained in Example 5 in which the surface layer portion was formed on the rough surface.
Further, Examples 3 and 4 having a distribution inclined in the layer thickness direction had higher adhesive strength than Examples 1 and 2 having a uniform distribution. However, the adhesive strengths of Examples 3 and 4 were slightly lower than those of Example 5.
For this reason, the difference depending on whether the distribution of the content of the inorganic particles 5 is uniform or inclined in the layer thickness direction, rather than the difference between the inorganic particles 5 being silica particles or TiO ₂ particles. Is big. Moreover, the difference of whether the surface layer part was formed on the rough surface is larger than the difference in the distribution of the content of the inorganic particles 5.
On the other hand, the comparative example 1 had much lower adhesive strength than the example 1 having the lowest adhesive strength.
In Comparative Example 2, the surface was hydrophilized, and thus the adhesive strength was higher than that of Comparative Example 1. However, since TiO ₂ was directly laminated on PEEK, the adhesion was poor, and the base material layer It was fractured at the upper surface 2a, and only about half the adhesive strength of Example ₂ with TiO ₂ on the surface was obtained.

  From the above results, when evaluated comprehensively, Examples 1 to 5 were evaluated as “◯ (good)”, and Comparative Examples 1 and 2 were evaluated as “× (no good)”.

1, 11, 21, 31 Resin member (resin member containing aromatic polyetherketone resin)
2, 22, 32 Base part 2a, 22a, 32a Base layer upper surface 3, 13, 23, 33 Surface layer part 3a, 13a, 23a, 33a Lower layer surface 3b, 13b, 23b Upper layer surface 4 Base resin layer 5 Inorganic particles (inorganic materials with hydrophilicity)
13A Lowermost layer 13B First intermediate layer 13C Second intermediate layer 13D Third intermediate layer 13E Fourth intermediate layer 13F Uppermost layer

Claims (4)

A base material portion made of a resin material mainly composed of an aromatic polyether ketone resin;
A surface layer portion laminated on the base material portion and mixed with an inorganic material having hydrophilicity in the resin material;
With
A resin member containing an aromatic polyether ketone resin, wherein the inorganic material is exposed on the surface of the surface layer portion opposite to the base material portion. The content of the inorganic material in the surface layer portion is
2. The resin member containing an aromatic polyether ketone resin according to claim 1, wherein the resin member has a distribution that increases from the base portion side toward the layer surface side in the layer thickness direction. The interface with the surface layer part in the base material part is
The resin member containing an aromatic polyether ketone resin according to claim 1, wherein the resin member has an uneven shape. The inorganic material is
The resin member containing an aromatic polyether ketone resin according to any one of claims 1 to 3, wherein the resin member is made of a particulate inorganic substance having a melting point higher than that of the aromatic polyether ketone resin.

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