TW201522062A - Grooved resin molding, composite molding, and composite molding manufacturing method - Google Patents

Abstract

The present invention makes it possible to adequately bond one resin molding with another molding even when, for example, the melting point of the resin of the one molding (resin molding) is lower than the molding temperature of the other molding. This grooved resin molding comprises an inorganic filler (11) and is obtained by forming multiple microgrooves (12) in which said inorganic filler (11) is exposed on the surface (10a) of said resin molding such that the ratio (W13:W12) of the width of the ridges (13), which are located between the microgrooves (12), to the width of the microgrooves (12) on the surface (10a) is 1: 1.5 - 5. The composite molding (1) is obtained by using the surface (10a) of such a grooved resin molding as the contact surface and disposing the other molding (20) adjacent thereto.

Description

Resin molded product having groove, composite molded product, and manufacturing method of composite molded product

The present invention relates to a resin molded article having a gully, a composite molded article using the resin molded article having the gully, and a method of producing the composite molded article.

In recent years, in the fields of automobiles, electrical products, industrial machines, and the like, in order to reduce carbon dioxide emissions and reduce manufacturing costs, the tendency to replace some of the metal molded articles with resin molded articles is expanding. Along with this phenomenon, a composite molded article in which a resin molded article and a metal molded article are integrated is widely spread. Further, the present invention is not limited thereto, and a composite molded article in which molded articles composed of the same type or different materials are integrated is also widely used.

A method for producing a composite molded article in which one molded article and another molded article are integrated is, for example, as follows. In other words, Patent Document 1 proposes to form a filler such as glass fiber in a resin constituting one of the molded articles, and to form a resin, a plasma, a flame, and the like on the surface of the resin which is next to the other molded article. After the resin having a thickness of several μm to several tens of μm is removed, another resin is placed adjacent to the surface of the other resin, filled and molded, and the subsequent method is carried out. Further, Patent Document 2 proposes to form a nanostructure on the surface by irradiating electromagnetic radiation on the surface of one of the resin molded articles, and then A method in which the other resin molded article is adjacent to the surface and filled and formed to form an integrated method.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 01-126339

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-529404

In addition, the inorganic filler is formed on the surface of the resin molded article (primary resin molded article) containing the inorganic filler, and the inorganic filler is exposed, and the material constituting the secondary molded article flows into the microgroove. Integration, and methods for manufacturing composite molded articles of increased strength have also been studied.

However, there is still room for improvement in the strength when joining a molded article to another molded article. Further, for example, in the case where a micro-groove is formed on the surface of a molded article, the melting point of the constituent resin of the molded article is lower than the forming temperature or melting point of the constituent material of the other molded article. When another molded article material (melt) flows into the surface of the product, the micro gully melts and is damaged, and the molten material of another molded product cannot be sufficiently entered in the micro gully, and the high sulcus may not be subjected to high strength. The case of joining.

The present invention has been made in view of the above circumstances, and it is an object of the invention to form one of the resins even if the melting point of the resin of the molded article (resin molded article) is lower than the molding temperature or melting point of the other molded article. The product is fully joined to another molded article.

The present inventors have made intensive studies to solve the above problems. As a result, it has been found that, for one of the resin molded articles, a part of the resin of the resin molded article containing the inorganic filler is removed, and on the surface of the resin molded article, the inorganic filler is exposed in a manner that the width of the groove is enlarged. Tiny gully. Thereby, even if the resin molded article (one molded article) having the groove has a melting point of the resin and is lower than the molding temperature or melting point of the other molded article constituent material, the material melt of the other molded article can be obtained. By fully and effectively flowing into the micro-groove, the anchor effect by the inorganic filler can be effectively exerted, and the present invention has been completed. That is, the present invention is provided as follows.

(1) The resin molded article having a gully according to the present invention is a micro-groove containing an inorganic filler and exposing the inorganic filler, and is on the surface of the resin molded article, and is located between the micro-grooves The ridge portion and the micro gully are formed on the surface at a width of 1:1.5 to 5.

(2) The invention according to the invention, wherein the inorganic filler protrudes from the side wall of the microgroove and is exposed.

(3) The invention of the present invention, wherein the micro-grooves are formed in a lattice shape on the surface of the invention.

(4) The invention of any one of (1) to (3), wherein the inorganic filler is a fibrous inorganic filler.

(5) Further, in the resin molded article having the gully of the present invention, (1) The invention according to any one of the preceding claims, wherein the gully is formed by laser irradiation.

(6) The resin molded article having the gully of the present invention, wherein the invention according to any one of (1) to (5) is provided on the surface on which the micro gully is provided, adjacent to another The molded article is formed into a composite molded article; and the molding temperature of the other molded article is higher than the melting point of the resin molded article constituting the grooved resin.

(7) The composite molded article of the present invention is a composite molded article, and the other surface of the resin molded article having the gully according to any one of the above (1) to (6) is disposed adjacent to each other. The melting point of the constituent material of the other molded article is higher than the constituent resin of the resin molded article having the groove.

(8) In the method of producing a composite molded article of the present invention, the surface of the first resin molded article containing the inorganic filler is disposed adjacent to each other, and the molding temperature is higher than the melting point of the resin of the first resin molded article. The second molded article, the method for producing a composite molded article of the composite molded article, comprising a groove forming step and a forming step, wherein the groove forming step is performed by the first resin molded article adjacent to the second molded article On the surface, the ridge portion located between the micro-grooves and the gully portion of the micro-groove are formed so that the width of the surface is 1:1.5 to 5, and the inorganic filler protrudes from the side wall. The micro-groove is formed by flowing a molten material of the second molded article constituent material onto the surface of the first resin molded article on which the micro-groove is formed, and solidifying.

(9) The method of manufacturing the composite molded article of the present invention, wherein the forming step is performed by forming one of the micro-grooves as a contact surface and flowing into the second molded article constituent material. Curing by injection molding And the steps of forming.

According to the present invention, even if the melting point of the resin of one molded article (resin molded article) is lower than the molding temperature or melting point of the other molded article, one of the resin molded articles can be sufficiently joined to the other molded article.

1‧‧‧Composite molded products

10‧‧‧Resin molded products with gullies

10'‧‧‧Preparation

10a‧‧‧Surface of resin molded articles with gullies

10a'‧‧‧ surface

11‧‧‧Inorganic filler

12‧‧‧ tiny gullies

12a‧‧‧Small side wall of micro gully

13‧‧‧ Ridge

20‧‧‧ Another molded product

50‧‧‧ a resin molded product

51‧‧‧ tiny gullies

60‧‧‧ Another molded product

70‧‧‧Composite molded products

D‧‧‧Deep

W ₁₂ , W ₁₃ ‧ ‧ width

Fig. 1 is an enlarged schematic cross-sectional view showing a resin molded article having a gully.

Fig. 2 is a schematic enlarged cross-sectional view showing a composite molded article.

Fig. 3 is an electron microscope (SEM) photograph of a resin molded article having a gully formed with micro gullies on the surface thereof, (A) is a photograph when a micro gully is formed in a stripe shape, and (B) is a microgroove formed in a lattice shape. A photo of the time.

Fig. 4 is an explanatory view showing a procedure for obtaining a composite molded article by overmolding (embedded molding).

In Fig. 5, (A) is a SEM photograph of a resin molded article having a gully produced in Example 1, and (B) is a SEM photograph of a resin molded article having a gullet manufactured in Comparative Example 1.

In Fig. 6, (A-1) and (A-2) are SEM photographs of a resin molded article having a gully after peeling off the secondary molded article from the composite molded article of Example 1; In the composite molded article of Comparative Example 1, an SEM photograph of a resin molded article having a gully after peeling off the secondary molded article.

In Fig. 7, (A) is a cross-sectional photograph obtained by an optical microscope of the composite molded article of Example 1, and (B) is a cross-sectional photograph obtained by an optical microscope of the composite molded article of Comparative Example 1.

Fig. 8 is a cross-sectional photograph of a composite molded article of Comparative Example 1 obtained by an optical microscope.

Hereinafter, an embodiment (hereinafter referred to as "this embodiment") of the present invention will be described in detail with reference to the drawings. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

<1. Resin molded article having a gully>

Fig. 1 is a schematic cross-sectional view showing a resin molded article 10 (also referred to as "resin molded article") having a groove according to the present embodiment. The resin molded article 10 having the gully contains the inorganic filler 11, and the micro gully 12 (also referred to as "ditch") exposing the inorganic filler 11 is formed in plural on the surface 10a of the resin molded article 10 having the gully. on.

Further, the resin molded article 10 having the gully is characterized in that the width W ₁₂ (the width on the surface 10a) of the plurality of minute gullies 12 formed on the surface 10a thereof is located between the plurality of micro gullies 12 the width W of the ridge 13 and the width of the fine groove ₁₃ of the canal 12 W ratio of _{12 (13} W: ₁₂ W), becomes 1: 1.5 to embodiment 5 is formed.

In the composite molded article 1 using the resin molded article 10, as shown in FIG. 2, the resin molded article 10 has a surface 10a on one side of the plurality of microgrooves 12 as a contact surface. It is formed by welding another molded article 20.

(resin)

The resin type is a resin removal method such as laser irradiation or chemical treatment. On the premise that the micro gully 12 is formed, the rest is not particularly limited. For example, those who form a gully by laser irradiation may be, for example, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), polyacetal (POM), etc. .

Further, the chemical treatment may be, for example, a decomposition treatment by an acid or a base, a dissolution treatment by a solvent, or the like. In the case of an amorphous thermoplastic resin, it is easier to dissolve in various solvents, but in the case of a crystalline resin, a disolvent is preferably used. For example, a gully can be formed by adding an acid or a base, and examples thereof include polybutylene terephthalate (PBT), polyacetal (POM), and the like. Among them, in the chemical treatment, it is important to perform chemical treatment only on the portion where the gully is formed, and then remove the product by chemical treatment.

Further, the resin may be thermoplastic or thermosetting.

(inorganic filler)

The inorganic filler 11 is formed by removing a part of the constituent resin of the resin molded article 10 having the gully and forming the micro gully 12, and is exposed to the micro gully 12, and is not particularly limited. The inorganic filler 11 is exposed in the space (in the groove) of the microgroove 12 from the side wall 12a of the microgroove 12 to be formed, and the resin molded article 10 having the groove is formed into a composite shape with the other molded article 20. In the case of the product 1, the function of suppressing the separation of the anchors can be exhibited (see Fig. 2). Moreover, by exposing the inorganic filler 11 to the microgrooves 12, the inorganic filler 11 itself can be prevented from falling off from the composite molded article 1.

The inorganic filler 11 is not particularly limited, and may be, for example, glass fiber, carbon fiber, whisker fiber, glass cullet, mica or the like.

Further, the length of the inorganic filler 11 is preferably a length in the longitudinal direction and longer than the short side direction of the microgroove 12 (the width direction of the cross-sectional view of Fig. 1) length. In other words, it is preferable that the length of the minor groove 12 in the short-side direction is shorter than the length of the inorganic filler 11 in the longitudinal direction. For example, if the shape is fibrous, it is preferable that the average fiber length is longer than the length of the minor groove 12 in the short side direction; if the shape is amorphous, plate-like or particulate, the long diameter (preferably the average particle diameter) is preferable. It is longer than the length of the short side of the micro gully 12.

In the present embodiment, the inorganic filler 11 exposed by the microgrooves 12 functions as an anchor for suppressing the destruction of the resin molded article 10 having the gully and the other molded article 20 as described above. Therefore, in order to achieve this function, for example, the relief ridges 13 formed by removing a part of the resin according to the laser irradiation portion and the non-irradiation portion are preferably erected (bridged) in the micro groove 12 Inorganic filler 11. Moreover, the inorganic filler 11 can be used in this manner, and the shape of the inorganic filler 11 is preferably fibrous. Further, in the unevenness formed on the resin, the concave portion belongs to the minute groove 12, and the convex portion interposed between the plurality of minute grooves 12 serves as the ridge 13.

The content of the inorganic filler 11 is not particularly limited, and is preferably in the range of 5 parts by weight or more and 80 parts by weight or less based on 100 parts by weight of the resin. When the content is less than 5 parts by weight, even if the inorganic filler 11 is exposed by the microgrooves 12, the anchor function for suppressing the resin molded article 10 having the gully and the other molded article 20 may not be sufficiently exhibited. The possibility. On the other hand, when the content exceeds 80 parts by weight, the resin molded article 10 having the gully may not have sufficient strength.

(Preferred commercial product of resin material containing inorganic filler 11)

In addition, the resin material containing the inorganic filler 11 is commercially available, such as PPS with glass fiber (product name: DURAFIDE® PPS 1140A7, polyplastic company) System), incorporated into fiberglass. PPS (product name: DURAFIDE® PPS 6165A7, manufactured by Polyplastics Co., Ltd.) of inorganic filler, LCP (product name: VECTRA® LCP E130i, manufactured by Polyplastics Co., Ltd.) incorporating glass fiber.

(mini gully)

The microgrooves 12 are formed plurally on the surface 10a of the resin molded article 10, and the inorganic filler 11 is exposed from the side wall (side surface) 12a. The micro-grooves 12 are formed by removing a part of the resin from the resin molded article 10, whereby the inorganic filler 11 can be exposed in a state of being protruded from the side wall 12a by removing a part of the resin.

In addition, as shown in FIG. 2, the resin molded article 10 having the groove is provided with one surface (surface 10a) of the micro groove 12 as a contact surface, and is integrated with another molded article 20 to produce a composite molded article. At 1 o'clock, the inorganic filler 11 was not exposed in the composite molded article 1. In the present specification, even when the inorganic filler 11 is not exposed in the composite molded article 1, when the other molded article 20 is removed from the composite molded article 1, the inorganic filler 11 is exposed from the microgrooves 12 In addition, it is still considered as "the inorganic filler 11 is exposed in the micro gully 12".

The longitudinal direction of the microgrooves 12 (the direction toward the depth side in the cross-sectional view of FIG. 1) is preferably different from the longitudinal direction of the inorganic filler 11. If the longitudinal direction of the gully 12 is the same as the longitudinal direction of the inorganic filler 11, there are cases where the ridges 13 formed by removing a part of the resin in accordance with the laser irradiation portion and the non-irradiation portion are not properly crossed. The possibility of the inorganic filler 11 is set. In this case, the inorganic filler 11 is easily detached from the resin molded article 10 having the gully, and the anchor function of suppressing the damage of the resin molded article 10 having the gully and the other molded article 20 may not be sufficiently exhibited. So, as shown in the cross section of Figure 1. As shown in the figure, it is preferable to form a microgroove 12 by performing laser irradiation or the like on the resin in such a manner that the longitudinal direction of the microgrooves 12 is different from the longitudinal direction of the inorganic filler 11.

However, a resin molded article having a small groove and having a gully (referred to as "a resin molded article 50" for convenience of explanation) is formed by the pair of gullies (for the sake of explanation) It is convenient to use one side of the "micro-ditch 51"), and another molded product (referred to as "another molded product 60" for convenience of explanation) is integrated and integrated to produce a composite molded article (for explanation) Convenient, it is called "composite molded product 70"). At this time, the resin constituting one resin molded article 50 may have a resin material having a melting point lower than that of the other molded article 60 to constitute a melting point of a material such as a resin (in detail, a molding temperature of another molded article 60). In this case, when a resin molded article 50 having a groove is melted and another molded article 60 is melted and filled (formed), the resin molded article 50 is melted due to a high forming temperature, resulting in a surface thereof. The wall in which the micro gullies 51 are formed collapses and is squeezed and broken. In this case, even if the inorganic filler is exposed in the microgroove 51, the molten material of the constituent material of the other molded article 60 does not sufficiently enter the microgroove 51, and the use of the inorganic filler cannot be sufficiently obtained. Anchor effect.

In the present embodiment, the microgrooves 12 formed on the resin molded article 10 having the gully are controlled by the width W _{12 of the} microgrooves 12 on the surface 10a of the resin molded article 10 having the gully. Within the established scope. Specifically, the ratio of the width W ₁₃ of the ridge 13 between the plurality of microgrooves 12 and the width W ₁₂ of the microgroove 12 (W ₁₃ : W ₁₂ ) is 1:1.5 to 5, and the microgroove is widened. The width of the gully of 12.

Here, the width W ₁₂ and the width W ₁₃ mean the width on the surface 10a of the resin molded article 10 having the groove, and the width (groove width) W _{12 of the} micro groove ₁₂ , as shown by the broken line X in Fig. 1 The indication refers to the opening of the gully 12, and the width of the gully portion on the surface (surface 10a) of the ridge 13 is extended (line one).

An electron micrograph of the resin molded article 10 having the gully forming the microgrooves 12 on the surface 10a shown in Fig. 3(A). As shown in FIG. 3(A), the resin molded article 10 having the groove widens the width (groove width) of the microgrooves _{12 so} that the ratio represented by W ₁₃ : W ₁₂ is 1:1.5 to 5. In the resin molded article 10 having the gully, by widening the groove width of the microgrooves 12, even if the melting point of the resin is lower than the molding temperature of the other molded article 20 or the melting point of the constituent material of the other molded article 20, It is still possible to form a sufficient space for the inflow of the constituent material of the other molded article 20. By this, before the micro-grooves 12 of the resin molded article 10 are melted and buried, the constituent material of the other molded article 20 can surely flow into the micro-grooves 12, and the inorganic filling exposed from the micro-grooves 12 can be exhibited. The anchoring effect caused by the agent 11 causes the other molded article 20 to be firmly adhered (joined).

In a specific example, one of the microgrooves 12 and the ridges 13 is set to one set (pitch) on the surface 10a of the resin molded article 10, and when the one pitch is 200 μm, for example, the ridge 13 can be used. The width W _{13 is} set to 80 μm, and the width W _{12 of the} microgrooves _{12 is} set to 120 μm (in addition, in this case, W ₁₃ : W ₁₂ = 1: 1.5). Further, in the case of a pitch of 200 μm, for example, the width W _{13 of the} ridge 13 can be set to 33.3 μm, and the width W _{12 of the} microgroove _{12 can} be set to 166.7 μm (in addition, in this case, it is about W ₁₃ : W ₁₂ = 1:5). ).

When the pitch between the microgrooves 12 and the ridges 13 is 300 μm, for example, the width W _{13 of the} ridges 13 can be 120 μm, and the width W _{12 of the} microgrooves _{12 can} be set to 180 μm (in addition, this case) Become W ₁₃ :W ₁₂ =1:1.5). Further, in the case of a pitch of 300 μm, the width W _{13 of the} ridge 13 can be set to 50 μm, and the width W _{12 of the} minute groove _{12 can} be set to 250 μm (in this case, W ₁₃ : W ₁₂ = 1:5).

In addition, the specific examples are merely illustrative, and are not limited thereto, so that the distance between the micro-grooves 12 and the ridges 13 can be matched in the range of W ₁₃ : W ₁₂ =1: 1.5 to 5 Make appropriate decisions. However, in consideration of appropriately obtaining the anchor effect, the pitch width of each of the microgrooves 12 and the ridges 13 is set to be one set, and preferably 100 μm or more and 500 μm or less, and more preferably 200 μm or more and 300 μm or less. When the pitch width is too narrow, the inorganic filler 11 is not exposed from the side surface of the microgrooves 12, and the anchoring effect by the inorganic filler 11 may not be appropriately obtained. When the width of the pitch is too wide, the inorganic filler 11 is easily detached from the resin molded article 10 having the gully, and the resin molded article 10 having the gully and the other molded article 20 are not sufficiently exhibited by the inorganic filler 11. The possibility of broken anchors.

The width W ₁₂ of the micro groove 12 on the surface 10a of the resin molded article 10 having the gully is not more than 1.5 times the width W ₁₂ of the ridge 13 is less than 1.5 times the width W ₁₃ of the ridge 13 when the other molded article 20 is welded. The resin molded article 10 having the gully is melted, and the wall of the micro gully 12 formed on the resin molded article 10 is collapsed and broken. On the other hand, when the width W ₁₂ of the micro groove 12 is more than 5 times the width W ₁₃ of the ridge 13, the anchor function by the inorganic filler 11 cannot be sufficiently exhibited, and an external force is applied to the composite molded article 1 to cause another The possibility that a molded article 20 is destroyed.

Further, the width W _{12 of the} related microgrooves 12 is preferably such that the ratio indicated by "W ₁₃ : W ₁₂ " is a width W ₁₂ of 1:2 to 4, and the microgrooves 12 are provided. By this, it is possible to more efficiently flow into the molten material of the other molded article 20 in the microgrooves 12 of the resin molded article 10 having the gully, and to further improve the anchoring effect, thereby forming a resin having high joint strength. Product 10.

Here, the micro-grooves 12 may be formed in a stripe shape as shown in FIG. 3(A) on the surface 10a of the resin molded article 10, or may be formed as a lattice in which the micro-grooves 12 are crossed as shown in FIG. 3(B). shape. When the microgrooves 12 are formed in a lattice shape, the longitudinal direction of the microgrooves 12 may be formed in a diagonal lattice shape different from the longitudinal direction of the inorganic filler 11. As shown in FIG. 3(B), the micro-grooves 12 are formed in a lattice shape, so that the molten material of the constituent material of the other molded article 20 can be more reliably flowed into the micro-grooves 12.

When the micro-grooves 12 are formed in a lattice shape, the width W ₁₂ of the micro-grooves 12 on the surface 10a thereof and the width W _{13 of the} ridges 13 are related to each other as long as the longitudinal direction of the lattice-shaped micro-grooves 12 is formed (for example, In the case of the x-axis direction of 3, the relationship between the micro-grooves 12 and the ridges 13 is satisfied as W ₁₃ : W ₁₂ = 1: 1.5 - 5. Further, when viewing the other longitudinal direction of the microgrooves 12 (for example, the y-axis direction in FIG. 3), the width of the microgrooves 12 and the ridges 13 is satisfied as W ₁₃ : W ₁₂ = 1: 1.5 - 5 Relationship can be.

Further, when the microgrooves 12 are formed in a lattice shape, the ratio of the width of the microgrooves 12 to the ridges 13 in one longitudinal direction (x-axis) and the other long-side direction (y-axis) of the microgrooves 12 It can be the same ratio or different ratios before satisfying the relationship of W ₁₃ :W ₁₂ =1:1.5~5, respectively.

The depth D of the microgrooves 12 is preferably 1/2 or more of the length in the short side direction of the microgrooves 12 (that is, the width W ₁₂ of the microgrooves ₁₂ ). When the depth D is less than 1/2 of the width W ₁₂ of the microgroove 12, when the composite molded article 1 is joined by joining another molded article 20, the inorganic filler 11 exposed in the microgroove 12 is formed into another shape. A sufficient anchoring effect cannot be produced between the products 20, and there is a possibility that the resin molded article 10 having the gully cannot be firmly adhered to the other molded article 20.

<2. Method for Producing Resin Molded Article with Gully>

In the resin molded article 10 having the gully, the resin molded article containing the inorganic filler 11 is subjected to laser irradiation, chemical treatment, or the like to partially remove the resin, and a plurality of minute gullies 12 are formed on the surface 10a of the resin molded article. You can get it. In the resin molded article 10 having the gully, the micro-grooves 12 are formed by partially removing the surface 10a of the resin molded article, and the inorganic filler 11 contained in the resin molded article is exposed from the side wall 12a of the micro-grooves 12.

The irradiation of the laser is set depending on the type of the material to be irradiated and the output of the laser device. If the micro-groove 12 is not formed by irradiating the resin with moderate energy, the inorganic filler 11 is not sufficiently exposed or formed to have a width as set. The small gully 12 of W ₁₂ and depth D tends to be difficult, and therefore it is preferable to perform the plural times separately.

In the present embodiment, when the microgrooves 12 are formed, the width W ₁₂ on the surface 10a of the resin molded article 10 having the groove is set to the width W ₁₃ of the ridge 13 between the plurality of microgrooves 12 and The ratio (W ₁₃ : W ₁₂ ) of the width W ₁₂ of the micro groove 12 is in the state of 1:1.5 to 5.

In the present embodiment, the micro groove 12 having the expanded width W ₁₂ is formed, and even if the resin molded article 10 constitutes the melting point of the resin and is lower than the molding temperature or melting point of the other molded article 20, Before the microgrooves 12 of the resin molded article 10 are melted and buried, the constituent resin of the other molded article 20 is caused to flow into the microgrooves 12. Thereby, the anchor effect by the inorganic filler 11 can be effectively produced, and the other molded article 20 can be sufficiently joined to the resin molded article 10.

Here, when the microgrooves 12 are formed by laser irradiation, the glass fibers used as the inorganic filler 11 partially shield the laser energy. Therefore, in order to remove the resin up to the depth and perform laser irradiation a plurality of times, it is necessary to give an energy that is absorbed by the laser beam to the exposed glass fiber or the like. Therefore, when the laser is repeatedly irradiated a plurality of times, it is preferable to include a step of increasing the amount of laser irradiation to be higher than the amount of the previous irradiation.

In addition, in order to remove the resin located on the back surface of the inorganic filler 11 having low laser light transmittance, the laser irradiation is preferably performed from a direction other than the vertical direction of the surface 10a of the resin molded article 10.

On the other hand, when the microgrooves 12 are formed by chemical treatment, an acid, a base, an organic solvent or the like which blends with the resin characteristics can be selected. The polyacetal resin molded article in which the resin is decomposed by the acid is decomposed and removed by an acid in a place where the micro gully is designed to form a gully. In addition, a non-crystalline resin molded article which is easily dissolved in an organic solvent is formed by masking a region other than the place where the micro-groove is designed on the surface of the molded article, and then dissolving and removing the organic solvent to form a gully.

<3. Composite molded article>

Fig. 2 is an enlarged schematic cross-sectional view showing the composite molded article 1 of the present embodiment. As shown in Fig. 2, in the composite molded product 1 in which the resin molded article 10 having the gully is provided with a surface (surface 10a) on one side of the microgroove 12 as a contact surface, and another molded article is placed adjacent to the surface. 20.

The other molded article 20 inside the micro gully 12 is not particularly limited, and in order to obtain a high anchor effect, it is preferable to use the inside of the micro gully 12 The other molded article 20 is disposed to surround the inorganic filler 11 .

(another molded product)

Here, when the other molded article 20 is in an uncured state, it can enter the micro-groove 12 of the resin molded article 10 from which the inorganic filler 11 is exposed, and the rest is not particularly limited, and for example, a curable resin (heat) A curable resin, a photocurable resin, a radiation curable resin, or the like), a thermoplastic resin, or the like. Further, it is not limited to the above resin, and may be a rubber, an adhesive, a metal or the like.

In the present embodiment, even when the molding temperature of the other molded article 20 (that is, the melt of the constituent material of the other molded article 20, the resin molded article 10 having the groove has a temperature at which the surface 10a of the microgroove 12 is formed) When the resin molded article 10 having the gully is formed to have a melting point of the resin (or the melting point of the other molded article 20 is higher than the melting point of the resin molded article 10), the melt can be surely flowed in at the same time. The microgroove 12 formed on the resin molded article 10 having the gully. That is, by expanding the width W _{12 of the} plurality of microgrooves 12 formed on the resin molded article 10 having the gully, the relationship of the width W ₁₃ of the ridge 13 located between the microgrooves 12 satisfies W ₁₃ :W _{In the state of 12} = 1 : 1.5 to 5, a sufficient space for allowing the constituent material of the other molded article 20 to flow into the microgroove 12 can be formed before the microgroove 12 is melted and buried. Thereby, the anchor effect by the inorganic filler 11 exposed from the microgrooves 12 can be effectively exhibited, and the other molded article 20 can be effectively joined.

For example, when the resin molded article 10 having the gully is combined with the material of the other molded article 20, when the constituent material of the resin molded article 10 having the gully is polyphenylene sulfide (PPS), for example, the molding temperature or the melting point is high. Another molded article 20 composed of a liquid crystal polymer (LCP), polyetheretherketone (PEEK) or the like is combined at the PPS melting point.

<4. Manufacturing method of composite molded article>

In the composite molded article 1 as described above, the surface (surface 10a) in which the microgrooves 12 are provided in the resin molded article 10 having the groove is a contact surface, and another molded article 20 is placed adjacent to the surface. The composite molded article 1 can be obtained by, for example, overmolding (embedded molding).

Hereinafter, a method of manufacturing the composite molded article 1 by overmolding will be described in detail. Here, a case where a resin such as a curable resin is used as a constituent material of another molded article is exemplified.

(Manufacture of composite molded article by overmolding)

Fig. 4 is a schematic view showing a method of obtaining a composite molded article 1 by overmolding. As shown in Fig. 4, first, the resin is molded once, and the preparation 10' of the resin molded article 10 having the gully is produced (Fig. 4 (1)).

Next, a part of the surface 10a' of the preparation 10' is subjected to partial removal of the resin, and a micro-groove 12 is formed in plural on the surface 10a' (Fig. 4 (2)). Thereby, the resin molded article 10 having the gully is obtained. In this case, in the present embodiment, the width W _{12 of the} plurality of microgrooves 12 is determined by the ratio of the width W ₁₃ of the ridge 13 between the microgrooves 12 and the width W ₁₂ of the microgroove 12 (W ₁₃ :W ₁₂ ) The method is 1:1.5~5, and the micro gully 12 is formed.

Next, as shown in Fig. 4 (3), the resin molded article 10 having the gully is placed in a mold (not shown), and a surface 10a on which the micro gully 12 is provided is used as a contact surface inside the mold. The secondary resin [unhardened material (melt) of the constituent material of the other molded article 20] is introduced and inserted (injection injection), and is hardened.

Here, the secondary resin (melt) is not particularly limited in the flow direction of the surface 10a of the resin molded article having the gully, and it is preferable to follow the tree having the gully The longitudinal direction of the microgrooves 12 formed on the fat molded article 10 flows in parallel in a parallel manner. When the secondary resin flows in the direction orthogonal to the longitudinal direction of the microgrooves 12, the walls of the microgrooves 12 are easily collapsed due to the flow of the secondary resin, and the possibility that the gullies are buried is improved. On the other hand, by flowing the secondary resin in a direction parallel to the longitudinal direction of the microgrooves 12, it is possible to suppress the melting and breakage of the microgrooves 12, and it is possible to more effectively cause the secondary resin to flow into the microgrooves 12 .

Through the above steps, the composite molded article 1 with the curable resin (the other molded article 20) can be obtained by overmolding. Further, in the same manner, by forming a thermoplastic resin which is heated and melted by a secondary resin, a composite molded article 1 with a thermoplastic resin can be obtained by overmolding.

[Examples]

Hereinafter, the embodiments of the present invention will be described, but the present invention is not limited to the embodiments. Further, in the following examples and comparative examples, three kinds of samples were produced in each of the examples (for example, three kinds of samples such as Examples 1-1 to 1-3 were produced according to the conditions of Example 1), and the following Table 1 was respectively used. The measured damage load (N) is shown.

"Manufacture of resin molded articles and composite molded articles having gullies"

[Example 1]

. Manufacture of resin molded articles having gullies

Using a glass fiber-containing PPS (DURAFIDE® PPS 1140A7, manufactured by Polyplastics Co., Ltd.) (melting point: about 280 ° C), injection molding was carried out under the following conditions to obtain an injection-molded article (resin molded article, primary molded article).

(DURAFIDE® PPS injection molding conditions)

Pre-drying: 140 ° C, 3 hours

Extrusion temperature: 320 ° C

Mold temperature: 140 ° C

Injection speed: 20mm/sec

Packing pressure: 50MPa (500kg/cm ² )

With respect to the obtained resin molded article, micro gullies were formed on the surface of the resin molded article by laser irradiation in accordance with the conditions shown in Table 1 below. Further, the depth of the microgrooves was set to 100 μm. Here, the "pitch" in Table 1 means the width of the groove portion of the micro groove on the surface of the resin molded article and the total width of the ridge portion on the side adjacent to the groove portion. In addition, "W ₁₃ : W ₁₂ " refers to the width ratio of the ridge portion (convex portion) to the groove portion (concave portion) when the width of the groove portion of the micro groove is W ₁₂ and the width of the ridge portion is W ₁₃ . In addition, the "small groove shape of the surface" means a micro groove shape on the surface of the resin molded article, and is "horizontal" as shown in Fig. 3(A) or "oblique lattice" as shown in Fig. 3(B).

In the first embodiment, a resin molded article having a gully is obtained by forming a striated micro-ditch of W ₁₃ : W ₁₂ = 40 μm: 160 μm (1:4) in a resin molded article at a pitch of 200 μm.

In addition, the conditions of the laser irradiation treatment are as follows.

(Laser irradiation conditions at the time of formation of micro gullies)

Oscillation wavelength: 1.064μm

Maximum rated output: 13W (average)

Laser output: 45%

Scanning speed: 1000mm/sec

Frequency: 40kHz

Rewrite: 40 times

※3 times at 30μm pitch

※ Preheating at 230 ° C × 3 hr

. Manufacturing of composite molded articles

In the resin molded article (primary molded article) having the gully obtained as described above, the surface on which the microgroove formed by the laser irradiation is provided is a contact surface, and the injection molding die is inserted, and the other molding is performed. The material of the product (secondary molded article) was subjected to injection molding using LCP (VECTRA® LCP E130i, manufactured by Polyplastics Co., Ltd.) under the following conditions to obtain a composite molded article.

(EXCTRA® injection molding conditions)

Pre-drying: 140 ° C, 4 hours

Extrusion temperature (forming temperature): 380 ° C

Mold temperature: 60 ° C

Injection speed: 200mm/sec

Packing pressure: 50MPa (500kg/cm ² )

[Embodiment 2]

In the second embodiment, a resin having a gully was produced in the same manner as in Example 1 except that the shape of the microgroove on the surface of the resin molded article was an oblique lattice shape at the time of production of the resin molded article having the gully. In the molded article, a composite molded article is produced from the obtained resin molded article having a gully.

[Example 3]

In the third embodiment, except for the production of a resin molded article having a gully, a ridge-like micro gully of W ₁₃ : W ₁₂ = 90 μm: 210 μm (1: 2.3) was formed at a pitch of 300 μm, and the others were carried out. In the same manner as in Example 1, a resin molded article having a gully was produced, and a composite molded article was produced from the obtained resin molded article having a gully.

[Example 4]

In the case of the production of the resin molded article having the gully, the resin having the gully was produced in the same manner as in Example 3 except that the shape of the microgroove on the surface of the resin molded article was an oblique lattice shape. In the molded article, a composite molded article is produced from the obtained resin molded article having a gully.

[Comparative Example 1]

In Comparative Example 1, except for the production of a resin molded article having a gully, a ridge-like micro-groove of W ₁₃ : W ₁₂ = 100 μm: 100 μm (1:1) was formed at a pitch of 200 μm, and the others were carried out. In the same manner as in Example 1, a resin molded article having a gully was produced, and a composite molded article was produced from the obtained resin molded article having a gully.

[Comparative Example 2]

In Comparative Example 2, except for the production of a resin molded article having a gully, an oblique lattice-shaped micro-groove of W ₁₃ : W ₁₂ = 100 μm: 100 μm (1:1) was formed at a pitch of 200 μm, and the others were implemented. In the same manner as in Example 1, a resin molded article having a gully was produced, and a composite molded article was produced from the obtained resin molded article having a gully.

"Evaluation"

<Magnification observation of resin molded article having gully>

In the resin molded article (primary molded article) having the gully of Example 1 and Comparative Example 1, one surface of the micro-groove was observed by an electron microscope (SEM). Fig. 5(A) is a SEM photograph of a resin molded article having a gully manufactured in Example 1. Fig. 5(B) is a SEM photograph of a resin molded article having a gully manufactured in Comparative Example 1. In addition, the magnification is set to 200 times.

As is apparent from the SEM photograph of FIG. 5(A), the first embodiment is provided with a resin molded article in which the microgrooves of the groove width (W ₁₃ : W ₁₂ = 1:4) are widened. On the other hand, as shown in the SEM photograph of FIG. 5(B), Comparative Example 1 is a resin molded article in which a gully portion and a ridge portion having a micro-groove having a width of 1:1 are provided.

<Enlarged observation after peeling and peeling another molded article (secondary molded article) from the composite molded article>

In the composite molded article of the first and the comparative examples, the resin molded article (primary molded article) having the gully when the secondary molded article (LCP) was peeled off from the composite molded article was observed by an electron microscope (SEM). surface. 6(A-1) (magnification: 200 times) and FIG. 6(A-2) (magnification: 50 times) are resin moldings having a gully after peeling off the secondary molded article from the composite molded article of Example 1. SEM photo of the product. Fig. 6 (B) (magnification: 200 times) is a SEM photograph of a resin molded article having a gully after peeling off the secondary molded article from the composite molded article of Comparative Example 1.

From the SEM photographs of FIGS. 6(A-1) and (A-2), when the composite molded article of Example 1 is peeled off and peeled off the secondary molded article, the resin molded article having the gully is formed with minute gullies. At the site, the stripe-like LCP looks the same as the shape of the micro gully. This phenomenon is a phenomenon in which a molten material that efficiently flows into a secondary molded product (LCP) in a micro-groove of a resin molded article having a gully, and an anchor effect caused by the glass fiber exposed in the micro-groove, The secondary molded article is sufficiently bonded to a resin molded article having a gully.

On the other hand, from the SEM photograph of Fig. 6(B), the composite molded article of Comparative Example 1 was peeled off and peeled off the secondary molded article, and there was no LCP residue at the portion where the micro gullies were formed. A part of the surface of the resin molded article remaining in the non-groove portion is hung. That is, this composite molded article can be said that the secondary molded article is not sufficiently joined. This phenomenon is considered to be carried out by forming an LCP having a molding temperature higher than the melting point of the resin molded article having the gully to form the melting point of the resin PPS. At the time of molding, the micro gullies of the resin molded article having the gully are melted and broken, and as a result, there is no molten material flowing into the LCP in the gully portion. Further, in the composite molded article of Comparative Example 1, when the secondary molded article was peeled off, the tester's hand was used to peel off very easily (see the result of breaking the load (N) described later).

<Expanded view of the cross section of the composite molded article>

The cross section of the composite molded article of Example 1 and Comparative Example 1 was observed by magnification with an optical microscope. Fig. 7(A) is a cross-sectional photograph showing the composite molded article of Example 1. Fig. 7(B) is a cross-sectional photograph of the composite molded article of Comparative Example 1. In addition, in FIG. 7, the lower layer of the cross-sectional photograph belongs to the PPS having the resin molded article of the gully, and the upper layer belongs to the LCP of the secondary molded product.

In the cross-sectional photograph of Fig. 7 (A), the composite molded article of the first embodiment is formed in a micro-groove formed on a resin molded article (primary molded article) having a gully, and is surely entered into a secondary molded article. LCP. On the other hand, as seen from the cross-sectional photograph of Fig. 7(B), in the composite molded article of Comparative Example 1, micro-grit melt fracture occurred during molding of the secondary molded article, and the primary molded article (PPS) and the secondary molded article were observed. (LCP) is in contact with the horizontal plane. That is, it is known that the micro-groove has melted and broken before the LCP enters the micro-groove formed on the PPS.

Further, Fig. 8 shows another cross-sectional photograph of the composite molded article of Comparative Example 1 observed by an optical microscope. As is clear from the cross-sectional photograph of Fig. 8, the composite molded article of Comparative Example 1 is formed on the surface of the resin molded article having the gully in accordance with the LCP flow (flow direction indicated by the arrow in the figure) belonging to the secondary molded article. The walls of the tiny gullies melt and collapse, and the tiny gullies are blocked. Moreover, it is known that PPS and LCP will exhibit doping and mixing as the micro-groove melts. Hehe. In this case, as shown in FIG. 7(B), a sufficient amount of LCP is not entered in the microgroove.

<Evaluation of joint strength (measurement of damage load)>

In order to evaluate the joint strength (joint strength of the primary molded article and the secondary molded article) of the composite molded article obtained in the examples and the comparative examples, the breaking load (tensile breaking load) (N) was measured. The joint strength measurement based on the damage load was measured by using a tension machine UTA-50kN (manufactured by ORIENTEC Co., Ltd.), and the peeling composite molded article (length 120 mm, width 20 mm, thickness 2 mm) was peeled off at a chuck speed of 1 mm/min. The measurement results of the breaking load (N) and the conditions for forming the microgrooves of the resin molded article having the gully are collectively described in Table 1 below.

Further, as described above, in the examples and the comparative examples, three kinds of samples were produced in each of the examples (for example, the conditions of the first embodiment are three kinds of samples such as Examples 1-1 to 1-3), and are as shown in Table 1 below. The breaking load (N) was measured.

As is apparent from the results shown in Table 1, the composite molded articles of Examples 1 to 4 had an average breaking load of 125 N or more, and it was confirmed that the composite molded article had sufficient joint strength. Among them, in the Example 2 and Example 4 in which the micro gullies were formed in a diagonal lattice shape, the fracture forms of all the samples were not peeled and broken, but were destroyed by the base material, and it was found that higher joint strength was obtained.

On the other hand, in the comparative examples 1 and 2 in which the width of the gully of the micro gully is not widened, W ₁₃ : W ₁₂ = 1:1, regardless of the shape of the micro gully, which is stripe or lattice, the breaking load is about 30~. Around 40N, it is a very low joint strength. This phenomenon is considered to be as shown in Fig. 7(B) and Fig. 8. Since the forming temperature at which the LCP belonging to the secondary molded article flows is higher than the melting point of the PPS, the micro gully is already melted and broken before the LCP inflows. There is no reason for the LCP to enter. Therefore, the anchoring effect by the glass fiber cannot be sufficiently exerted, and it is judged that the bonding strength is low.

10‧‧‧Resin molded products with gullies

10a‧‧‧ surface

11‧‧‧Inorganic filler

12‧‧‧ tiny gullies

12a‧‧‧ Sidewall

13‧‧‧ Ridge

W ₁₂ , W ₁₃ ‧ ‧ width

D‧‧‧Deep

Claims (9)

A resin molded article having a gully, comprising an inorganic filler and a micro gully exposing the inorganic filler, and a ridge between the micro gully and the micro groove on the surface of the resin molded article漕, the width of the above surface is formed in a ratio of 1:1.5 to 5. The resin molded article having a gully according to the first aspect of the invention, wherein the inorganic filler protrudes from the side wall of the microgroove and is exposed. The resin molded article having a gully according to claim 1 or 2, wherein the micro gully is formed in a lattice shape on the surface. The resin molded article having a gully according to any one of claims 1 to 3, wherein the inorganic filler is a fibrous inorganic filler. The resin molded article having a gully according to any one of claims 1 to 4, wherein the micro gully is formed by laser irradiation. The resin molded article having a gully according to any one of claims 1 to 5, wherein a composite molded article is formed by arranging another molded article adjacent to a surface on which the microgroove is provided; The molding temperature of the other molded article is higher than the melting point of the resin of the resin molded article having the groove. In the composite molded article, the other molded article is disposed adjacent to the surface of the resin molded article having the gully according to any one of claims 1 to 6; and the other molded article constitutes the melting point of the material. A constituent resin higher than the resin molded article having the gully. In the method of producing a composite molded article, a second molded article comprising a melting point of a resin having a higher molding temperature than the resin of the first resin molded article is disposed adjacent to the surface of the first resin molded article containing the inorganic filler to form a composite. to make The method for producing a composite molded article of the shaped product includes a gully forming step of arranging the ridge between the microgrooves on the surface of the first molded article adjacent to the second molded article The gully portion of the micro-groove has a micro-groove in which the inorganic filler protrudes from the side wall so that the width of the surface is 1:1.5 to 5, and a forming step of forming the micro-groove On the surface of the first resin molded article, a molten material that has flowed into the second molded article constituent material is solidified and molded. The method of producing a composite molded article according to the eighth aspect of the invention, wherein the forming step is performed by forming one of the microgrooves as a contact surface, flowing into the second molded article constituent material, and solidifying and molding by injection molding. step.