TWI610809B - Resin molded product having groove, composite molded product, and manufacturing method of composite molded product - Google Patents

Abstract

Even if the resin melting point of one molded product (resin molded product) is lower than the molding temperature of the other molded product, for example, one of the resin molded products can be sufficiently bonded to the other molded product.

The resin-molded article having a gully according to the present invention is a micro-gully 12 containing an inorganic filler 11 and exposing the inorganic filler 11. The surface of the resin-molded product 10 a is plural and located in the micro-gully 12. The ridges 13 and the minute grooves 12 are formed on the surface 10a at a ratio of 1: 1.5 to 5 (W ₁₃ : W ₁₂ ). In addition, the composite molded product 1 uses the surface 10a of the resin molded product having such grooves as a contact surface, and another molded product 20 is disposed adjacently.

Description

Grooved resin molded product, composite molded product, and manufacturing method of composite molded product

The present invention relates to a resin molded article having a groove, a composite molded article using the resin molded article having a groove, and a method for manufacturing the composite molded article.

In recent years, in areas such as automobiles, electrical products, and industrial equipment, in response to calls for reduction of carbon dioxide emissions and reduction of manufacturing costs, the trend to replace part of metal molded products with resin molded products is expanding. In accordance with this phenomenon, composite molded products in which resin molded products and metal molded products are integrated are becoming widespread. Moreover, it is not limited to this, and the composite molded article which integrated the molded article which consists of the same or different material is spreading widely.

A method for manufacturing a composite molded product that integrates one molded product with another molded product is, for example, as described below. That is, Patent Document 1 has proposed a method in which fillers such as glass fiber are mixed into a resin constituting one of the molded products and formed, and a treatment such as a drug, a plasma, and a flame is performed on a surface of the resin that will subsequently constitute the other molded product. After removing the resin with a thickness of a few tenths of a μm to several tens of μm, the next method is to abut the other resin on the surface next to the other resin and fill and mold it. Further, Patent Document 2 has proposed a method in which a surface of one of the resin molded articles is irradiated with electromagnetic radiation to form a nanostructure on the surface, and then A method in which another resin molded product is abutted on the surface, and is filled and molded to integrate.

[Advanced technical literature] [Patent Literature]

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

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

In addition, micro-grooves are formed on the surface of a resin-molded product (primary resin-molded product) containing an inorganic filler to expose the inorganic filler, and the material constituting the secondary molded product is caused to flow into the micro-grooves. It is integrated, and the method of manufacturing a composite molded product with enhanced strength has also been studied.

However, there is still room for improvement in the strength when joining one molded product to another molded product. Further, for example, as described above, even when a minute groove is formed on the surface of one molded product, when the melting point of the constituent resin of the one molded product is lower than the molding temperature or melting point of the constituent material of the other molded product, When another molded product material (melt) flows on the surface of the product, the micro grooves will be melted and damaged, and the molten material of the other molded product cannot be sufficiently entered in the micro grooves. Joining situation.

This invention is made in view of the said situation, The objective is, for example, even if the resin melting point of one molded article (resin molded article) is lower than the molding temperature or melting point of the other molded article, one of the resins can be molded The product is fully bonded to another molded product.

The present inventors have intensively studied to solve the above problems. As a result, it was found that, for one of the resin molded products, a part of the resin of the resin molded product containing the inorganic filler was removed, and then on the surface of the resin molded product, a plurality of grooves were formed so as to expand the groove width to form an exposed inorganic filler. Tiny gully. Thereby, even if the melting point of the resin constituting the resin molded product (one molded product) having grooves is lower than the molding temperature or melting point of the material constituting the other molded product, the material melt of the other molded product can still be made. By fully and effectively flowing into the tiny gully, the anchor effect caused by the inorganic filler can be effectively exerted, and the present invention has been completed. That is, the present invention provides the following.

(1) The resin-molded article with a gully according to the present invention is a micro-gully that contains an inorganic filler and exposes the inorganic filler. The ridges and the minute grooves are formed so that the width of the surface is 1: 1.5 to 5 ratio.

(2) Furthermore, the resin molded article having a trench according to the present invention is the invention according to (1), wherein the inorganic filler is protruded and exposed from a side wall of the minute trench.

(3) Furthermore, the resin molded article having a trench according to the present invention is the invention according to (1) or (2), in which the micro trenches are formed in a grid shape on the surface.

(4) Furthermore, the resin molded article having a trench according to the present invention is the invention according to any one of (1) to (3), wherein the inorganic filler is a fibrous inorganic filler.

(5) Furthermore, the resin molded article having a trench according to the present invention is (1) The invention according to any one of (4), wherein the gully is formed by laser irradiation.

(6) Furthermore, the resin molded article having a gully according to the present invention is the invention according to any one of (1) to (5), which is provided on a surface provided with the above-mentioned microgully, and is arranged adjacent to another The molded product is formed into a composite molded product. The molding temperature of the other molded product is higher than the melting point of the resin constituting the resin molded product with grooves.

(7) Furthermore, the composite molded product of the present invention is a composite molded product, and another molding is disposed adjacent to the surface of the resin molded product having a trench according to any one of (1) to (6). The melting point of the constituent material of the other molded product is higher than that of the constituent resin of the resin molded product having grooves.

(8) Furthermore, the method for producing a composite molded product of the present invention is formed on the surface of a first resin molded product containing an inorganic filler, and is disposed adjacently to each other by a molding temperature higher than the resin melting point of the first resin molded product. A method for manufacturing a composite molded product that forms a composite molded product includes a ditch formation step and a molding step, wherein the ditch formation step is performed when the first resin molded product is adjacent to the second molded product. On the surface, a plurality of ridges located between the micro-gully and the gully of the micro-gully are formed so that the width of the surface becomes a ratio of 1: 1.5 to 5 so that the inorganic filler is protruded from the side wall. Micro grooves: This molding step is performed on the surface of the first resin molded product forming the micro grooves, and the molten material of the second molded product constituent material flows into the molten material and is solidified to be molded.

(9) Furthermore, in the method for producing a composite molded product according to the present invention, in the invention of (8), the molding step is performed by using one surface having the minute grooves as a contact surface and flowing into the second molded product constituent material, Curing by injection molding And forming steps.

According to the present invention, even if the resin melting point of one molded product (resin molded product) is lower than the molding temperature or melting point of the other molded product, one of the resin molded products and the other molded product can be sufficiently bonded.

1‧‧‧ composite molded product

10‧‧‧Resin molded article with groove

10'‧‧‧Preparation

10a‧‧‧ Surface of a resin molded article with grooves

10a'‧‧‧ surface

11‧‧‧ inorganic filler

12‧‧‧Mini Gully

12a‧‧‧Sidewall of Micro Gully

13‧‧‧ridge

20‧‧‧ Another molded product

50‧‧‧One resin molded product

51‧‧‧Micro Gully

60‧‧‧ Another molded product

70‧‧‧ composite molded product

D‧‧‧ Depth

W ₁₂ 、 W ₁₃ ‧‧‧Width

FIG. 1 is a schematic enlarged cross-sectional view of a resin molded product having a trench.

Fig. 2 is a schematic enlarged sectional view of a composite molded product.

Fig. 3 is an electron microscope (SEM) photograph of a resin molded product having a trench with micro trenches formed on its surface. (A) is a photograph when a micro trench is formed in a stripe pattern, and (B) is a micro trench formed in a grid pattern. Timely photos.

FIG. 4 is an explanatory diagram of a step when a composite molded product is obtained by stack mold molding (embedding molding).

In FIG. 5, (A) is a SEM photograph of a resin-molded article having grooves produced in Example 1, and (B) is a SEM photograph of a resin-molded article having grooves produced in Comparative Example 1.

In FIG. 6, (A-1) and (A-2) are SEM photographs of a resin molded product having grooves after tearing and peeling off the secondary molded product from the composite molded product of Example 1; (B) is from An SEM photograph of a resin molded article having grooves after the secondary molded article was torn apart and peeled off from the composite molded article of Comparative Example 1.

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 with an optical microscope.

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

<1. Resin-molded product having grooves>

FIG. 1 is a schematic cross-sectional view of a resin-molded article 10 (also referred to as a “resin-molded article”) having a trench in the present embodiment. The grooved resin molded product 10 contains an inorganic filler 11, and minute grooves 12 (also referred to as “gully grooves”) that expose the inorganic filler 11 are formed in plural on the surface 10 a of the grooved resin molded product 10. on.

Furthermore, the resin molded article 10 having a gully is characterized in that the width W ₁₂ (the width on the surface 10 a) of the plurality of micro gullies 12 formed on the surface 10 a 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 addition, as will be described in detail later, as shown in FIG. 2, the composite molded product 1 using the resin molded product 10 is a surface in which the resin molded product 10 has one of the plurality of minute grooves 12 as a contact surface. It is formed by welding another molded product 20.

(Resin)

Resin types are resin removal methods using laser irradiation or chemical treatment On the premise that the micro trenches 12 are formed, the rest are not particularly limited. For example, those who can form gully by laser irradiation, such as: polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), polyacetal (POM), etc. .

The chemical treatment system may be, for example, a decomposition treatment using an acid or an alkali, a dissolution treatment using a solvent, or the like. In the case of non-crystalline thermoplastic resins, it is easier to dissolve in various solvents, but in the case of crystalline resins, two solvents are selected. For example, those who can form furrows by adding acid or alkali can be, for example, polybutylene terephthalate (PBT), polyacetal (POM), and the like. Among them, it is important that the chemical treatment is performed only at the site where the gully is formed, and then the chemical treatment is used to remove the product.

The resin system may be thermoplastic or thermosetting.

(Inorganic filler)

The inorganic filler 11 is not particularly limited on the premise that the microgroove 12 is formed by removing a part of the constituent resin of the resin molded article 10 having the groove, and is exposed to the microgroove 12. The inorganic filler 11 is exposed from the side wall 12 a of the formed micro trench 12 in the space of the micro trench 12 (inside the trench). When the resin molded product 10 having the trench is formed into a composite molding with another molded product 20 In the case of the first product, it can exert the function of suppressing the occurrence of such an anchor (see FIG. 2). Furthermore, by exposing the inorganic filler 11 to the minute grooves 12 in this way, the inorganic filler 11 itself can be prevented from falling off from the composite molded product 1.

The inorganic filler 11 is not particularly limited, and examples thereof include glass fibers, carbon fibers, whisker fibers, glass fragments, and mica.

In addition, the length of the inorganic filler 11 is preferably the length in the long side direction, which is longer than the short side direction of the minute trenches 12 (the width direction of the cross-sectional view in FIG. 1). length. In other words, the length in the short-side direction of the micro trenches 12 is preferably shorter than the length in the long-side direction of the inorganic filler 11. For example, if the shape is fibrous, the average fiber length is preferably longer than the length in the short-side direction of the microgroove 12; if the shape is irregular, plate-shaped, or granular, the longer diameter is preferred (preferably the average particle diameter) It is longer than the short-side direction length of the micro trench 12.

In the present embodiment, the inorganic filler 11 exposed by the minute grooves 12 functions as anchors to suppress the destruction of the resin molded product 10 and another molded product 20 having the grooves as described above. Therefore, in order to achieve this function, for example, a part of the resin is removed according to the laser irradiation part and the non-irradiation part, and the concave-convex ridges 13 formed between the micro-grooves 12 are preferably bridged (bridged) to expose them. Inorganic filler 11. From the viewpoint that the inorganic filler 11 can be used, the shape of the inorganic filler 11 is preferably fibrous. In addition, as for the unevenness formed on the resin, the concave portion belongs to the minute grooves 12, and the convex portion sandwiched by the plurality of minute grooves 12 becomes the ridge 13.

The content of the inorganic filler 11 is not particularly limited, but it is preferably within a range of 5 parts by weight to 80 parts by weight based on 100 parts by weight of the resin. If the content is less than 5 parts by weight, even if the inorganic filler 11 is exposed by the minute grooves 12, the anchor function of suppressing the destruction of the resin molded product 10 and another molded product 20 having the grooves may not be fully exerted. Possibility. On the other hand, if the content exceeds 80 parts by weight, there is a possibility that the resin molded article 10 having grooves cannot have sufficient strength.

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

In addition, resin materials containing the inorganic filler 11 are commercially available such as glass fiber-doped PPS (product name: DURAFIDE® PPS 1140A7, Polyplastics Corporation) System), doped with glass fiber. Inorganic filler PPS (product name: DURAFIDE® PPS 6165A7, manufactured by Polyplastics Corporation), glass fiber-containing LCP (product name: VECTRA® LCP E130i, manufactured by Polyplastics Corporation), and the like.

(Miniature Gully)

The minute grooves 12 are formed in plural on the surface 10 a of the resin molded product 10, and the inorganic filler 11 is exposed from the side wall (side surface) 12 a. The minute groove 12 is formed by removing a part of the resin from the resin molded product 10, and by removing a part of the resin, the inorganic filler 11 can be exposed in a state protruding from the side wall 12a.

In addition, as shown in FIG. 2, a composite molded product is manufactured by using one surface (surface 10 a) of the micro-ditch 12 as the contact surface of the resin molded product 10 having the trenches, and integrating the molded product 20 with another molded product 20. At 1 hour, the inorganic filler 11 was not exposed in the composite molded product 1. In this specification, even when the inorganic filler 11 is not exposed in the composite molded product 1, if the other molded product 20 is removed from the composite molded product 1, the inorganic filler 11 is exposed from the minute grooves 12. If this is the case, it is still regarded as "the inorganic filler 11 is exposed in the minute trenches 12".

It is preferable that the long-side direction (direction toward the depth side in the cross-sectional view of FIG. 1) of the minute trench 12 is different from the long-side 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 will be, for example, irregular ridges 13 formed by removing a part of the resin in accordance with the laser-irradiated and non-irradiated portions, and cannot properly cross The possibility of the inorganic filler 11 is assumed. In this way, the inorganic filler 11 is likely to fall off from the resin molded product 10 having a groove, and there is a possibility that the anchor function of suppressing the destruction of the resin molded product 10 with another groove and the other molded product 20 cannot be sufficiently exerted. So, as shown in the section of Figure 1. As shown in the figure, it is preferable that the micro-trench 12 is formed by subjecting the resin to laser irradiation or the like in a manner that the long-side direction of the micro-trench 12 is different from that of the inorganic filler 11.

However, a resin molded product having one of the grooves (for convenience of explanation, referred to as "a resin molded product 50") having micro grooves formed has been formed. Conveniently, it is called "micro-groove 51"), and it is welded with another molded product (for convenience of description, called "another molded product 60") and integrated to manufacture a composite molded product (for illustration Convenient, called "composite molded product 70"). At this time, the resin constituting one resin molded product 50 may use a resin material having a melting point lower than the melting point of materials such as the resin constituting the other molded product 60 (more specifically, the molding temperature of the other molded product 60). In this case, when one molded resin product 50 having a groove is melted and filled (molded) with the other molded product 60, the one molded resin 50 may be melted due to a high molding temperature, resulting in the formation on the surface thereof. The wall of the formed micro-trench 51 collapses, squeezes, and breaks. As a result, even if the inorganic filler is exposed in the minute groove 51, the minute groove 51 does not sufficiently enter the molten material of the constituent material of the other molded product 60, and the use of the inorganic filler cannot be fully obtained. Anchor effect.

Here, in this embodiment, the width of the minute grooves 12 formed on the surface 10a of the resin molded article 10 having grooves is controlled by the width W ₁₂ of the minute grooves 12 formed on the resin molded article 10 having grooves. Within the given range. Specifically, the ratio of the width W ₁₃ of the ridge 13 between the plurality of micro trenches 12 and the width W ₁₂ of the micro trenches 12 (W ₁₃ : W ₁₂ ) is 1: 1.5 to 5, and the micro trenches are widened. Gully width of 12.

Here, the width W ₁₂ and the width W ₁₃ refer to the width on the surface 10 a of the resin molded article 10 having the grooves, and the width (the groove width) W _{12 of the} minute grooves 12 is as shown by the dotted line X in FIG. 1. Indicates that the width of the gully portion on the extension (surface 1) of the surface (surface 10a) of the ridge 13 refers to the opening of the gully 12.

FIG. 3 (A) shows an electron microscope photograph of a resin-molded article 10 having a groove formed on the surface 10a of the system. As shown in FIG. 3 (A), the resin molded product 10 having grooves widens the width of the minute grooves 12 (ditch width) so that the ratio represented by W ₁₃ : W ₁₂ becomes 1: 1.5 to 5. By forming a resin molded product 10 having a trench, the width of the trench of the micro trench 12 is widened, even if the melting point of the resin is lower than the molding temperature of the other molded product 20 or the melting point of the constituent material of the other molded product 20, It is still possible to form a sufficient space for the other molded product 20 to flow in the constituent material. Thereby, before the micro-trench 12 of the resin molded product 10 is melted and buried, the constituent materials of another molded product 20 can surely flow into the micro-trench 12, and the inorganic filling exposed from the micro-trench 12 can be utilized. The anchor effect caused by the agent 11 can make another molded product 20 firmly adhere (join).

As a specific example, on the surface 10a of the resin molded product 10, each of the minute grooves 12 and the ridges 13 is set as a group (pitch). When the 1 pitch is 200 μm, for example, the ridge 13 can be set. The width W _{13 is} set to 80 μm, and the width W _{12 of the} minute grooves _{12 is} set to 120 μm (in this case, W ₁₃ : W ₁₂ = 1: 1.5). When the pitch is 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} micro-trench _{12 can} be set to 166.7 μm (in this case, it is about W ₁₃ : W ₁₂ = 1: 5). ).

When the pitch between the micro-trench 12 and the ridge 13 is 300 μm, for example, the width W _{13 of the} ridge 13 can be set to 120 μm, and the width W _{12 of the} micro-trench _{12 can} be set to 180 μm (in addition, in this case) It becomes W ₁₃ : W ₁₂ = 1: 1.5). When the pitch is 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, these specific examples are at best only for illustration, and are not limited to this. In the range of W ₁₃ : W ₁₂ = 1: 1.5 ~ 5, the distance between the micro-trench 12 and the ridge 13 can be matched. Make the appropriate decision. However, if it is considered to obtain the anchor effect appropriately, the pitch width of each of the micro trenches 12 and the ridges 13 is set as a group, preferably 100 μm or more and 500 μm or less, more preferably 200 μm or more and 300 μm or less. If the pitch width is too narrow, the inorganic filler 11 will not be exposed from the side of the minute trenches 12, and there is a possibility that the anchor effect caused by the inorganic filler 11 cannot be obtained properly. If the width of the pitch is too wide, the inorganic filler 11 is likely to fall off from the resin-molded article 10 having grooves, and the inorganic filler 11 cannot sufficiently exert the effect of suppressing the resin-molded article 10 having grooves and another molded product 20 from being damaged. The possibility of a broken anchor function.

Related grooves, or channels having fine resin molded article 10 on the watercourse groove surface 10a a width W ₁₂ 12, 12 when the micro canal groove width W ₁₂ pair of ridges 13 is less than 1.5 times the width W is _13, when another when the molded product 20 will weld The resin molded article 10 having the grooves is melted, and the walls of the minute grooves 12 formed on the resin molded product 10 are collapsed and damaged. On the other hand, if the width W ₁₂ of the micro-trench 12 is more than 5 times the width W ₁₃ of the ridge 13, the anchor function of the inorganic filler 11 cannot be fully exerted, and external force may be applied to the composite molded product 1 to cause another Possibility of damage to one molded product 20.

Furthermore, the width W _{12 of the} related micro-trench 12 is more preferably such that the ratio of “W ₁₃ : W ₁₂ ” becomes the width W ₁₂ of 1: 2 to 4, and the micro-trench 12 is provided. Thereby, the micro-groove 12 of the resin-molded article 10 having the groove can be more effectively flowed into the constituent melt of another molded product 20, and the anchor effect can be further improved, and the resin can be molded with high bonding strength.品 10。 Product 10.

Here, the micro-trench 12 may form a stripe shape as shown in FIG. 3 (A) on the surface 10a of the resin molded product 10, or may form a grid in which the micro-trench 12 crosses as shown in FIG. 3 (B). shape. When the micro trenches 12 are formed in a grid shape, a diagonal grid shape in which the longitudinal direction of the micro trenches 12 is different from that of the inorganic filler 11 may also be formed. As shown in FIG. 3 (B), by forming the microgrooves 12 into a grid shape, it is possible to more surely cause the molten material constituting another molded product 20 to flow into the microgrooves 12.

When the micro-trench 12 is formed in a grid shape, the width of the micro-trench 12 on the surface 10a is related to the width W ₁₂ and the width _{13 of the} ridge 13. In the x-axis direction in 3), it is sufficient that the widths of the micro-trench 12 and the ridge 13 satisfy the relationship of W ₁₃ : W ₁₂ = 1: 1.5 to 5. In addition, when looking at the other long side direction of the micro-trench 12 (for example, the y-axis direction in FIG. 3), as long as the width of the micro-trench 12 and the ridge 13 is W ₁₃ : W ₁₂ = 1: 1.5 to 5 The relationship is all right.

In addition, when the micro trenches 12 are formed into a grid shape in this manner, the width ratio of the micro trenches 12 to the ridges 13 in one of the longitudinal directions (x axis) and the other longitudinal direction (y axis) of the micro trenches 12. It is mentioned before satisfying the relationship of W ₁₃ : W ₁₂ = 1: 1.5 ~ 5, which may be the same ratio or different ratios.

The depth D of the micro trenches 12 is preferably more than 1/2 of the length in the short side direction of the micro trenches 12 (that is, the width W _{12 of the} micro trenches ₁₂ ). When the depth D is less than 1/2 of the width W ₁₂ of the micro-trench 12, when the other molded product 20 is joined to form the composite molded product 1, the inorganic filler 11 exposed in the micro-trench 12 and another molding are formed. The sufficient anchor effect cannot be generated between the products 20, and there is a possibility that the resin molded product 10 having grooves cannot be firmly adhered to another molded product 20.

<2. Method for manufacturing a resin-molded product having a trench>

The resin molded product 10 having grooves is formed by applying a laser irradiation, a chemical treatment, etc. to the resin molded product containing the inorganic filler 11 to partially remove the resin, thereby forming a plurality of minute grooves 12 on the surface 10a of the resin molded product. Get it. The resin-molded article 10 having a groove is formed by removing the surface 10a of the resin-molded article to form the micro-groove 12 in such a manner that the inorganic filler 11 contained in the resin-molded article is exposed from the side wall 12a of the micro-groove 12.

The laser irradiation is set according to the type of material to be irradiated, the output of the laser device, and the like. If the resin is irradiated with moderate energy and the micro trenches 12 cannot be formed, the inorganic filler 11 will not be fully exposed or the width will be as set. W ₁₂ and micro-ditch ₁₂ of depth D tend to be difficult, so it is better to perform it several times separately.

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

In this embodiment, by forming the minute grooves ₁₂ with the expanded width W ₁₂ in this way, even if the resin molded product 10 constitutes the melting point of the resin, it is still lower than the molding temperature or melting point of the other molded product 20. Before the minute gully 12 of the resin molded product 10 is melted and buried, the constituent resin of another molded product 20 is caused to flow into the small gully 12. Accordingly, the anchor effect caused by the inorganic filler 11 can be effectively generated, and the other molded product 20 can be sufficiently bonded to the resin molded product 10.

Here, when the minute trenches 12 are formed by laser irradiation, glass fiber or the like used as the inorganic filler 11 partially shields the laser energy. Therefore, if the laser irradiation is performed a plurality of times in order to remove the resin to the depth, it is necessary to provide more energy that is absorbed due to the impact of the laser against the exposed glass fiber. Therefore, when the laser is repeatedly irradiated a plurality of times, it is preferable to include a step of increasing the laser irradiation amount to be higher than the previous irradiation amount.

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

On the other hand, when the micro-trench 12 is formed by a chemical treatment, an acid, an alkali, an organic solvent, and the like, which match the characteristics of the resin, can be selected. A polyacetal resin molded product that decomposes a resin with an acid can form a gully by decomposing and removing the place where a minute gully is designed with an acid. In addition, the amorphous resin molded article that is easily soluble in an organic solvent can be formed by masking areas other than the area where the minute grooves are designed in advance on the surface of the molded article, and then dissolving and removing the organic solvent.

<3. Composite molded products>

FIG. 2 is a schematic enlarged sectional view of a composite molded product 1 according to this embodiment. As shown in FIG. 2, the composite molded product 1 is a resin molded product 10 having a gully, and a surface (surface 10 a) on which one side of the minute gully 12 is provided is a contact surface, and another molded product is disposed adjacent to the surface. 20.

The shape of the other shaped product 20 inside the micro-gully 12 is not particularly limited. In order to obtain a high anchor effect, it is best to The other molded product 20 is arranged so as to surround the inorganic filler 11.

(Another molded product)

Here, the other molded product 20 is in the uncured state and can enter the minute grooves 12 of the resin molded product 10 that exposes the inorganic filler 11, and the rest is not particularly limited. For example, a curable resin (thermal (Curable resin, photocurable resin, radiation curable resin, etc.), thermoplastic resin, and the like. In addition, the resin is not limited to the resin described above, and may be rubber, an adhesive, a metal, or the like.

In this embodiment, even the molding temperature of the other molded product 20 (that is, the temperature at which the molten material constituting the other molded product 20 flows into the resin molded product 10 having the grooves and has the surface 10a forming the minute grooves 12) In the case where the melting point of the resin constituting the resin molded article 10 having the groove is higher (or the melting point of another molded article 20 is higher than the melting point of the resin molded article 10), the molten material can surely flow into The minute grooves 12 formed on the resin molded article 10 having the grooves. That is, by expanding the width W _{12 of the} plurality of minute grooves 12 formed on the resin molded product 10 having the grooves, the relationship with the width W ₁₃ of the ridges 13 located between the minute grooves 12 satisfies W ₁₃ : W _{In the state of 12} = 1: 1.5 ~ 5, a sufficient space can be formed for the constituent materials of another molded product 20 to flow into the micro-trench 12 before the micro-trench 12 is melted and buried. Thereby, the anchor effect caused by the inorganic filler 11 exposed from the micro trenches 12 can be effectively exerted, and another molded product 20 can be effectively joined.

For example, when the material of the resin molded product 10 having a gully is combined with another molded product 20, when the constituent material of the resin molded product 10 with a gully is polyphenylene sulfide (PPS), the molding temperature or melting point may be high, for example. At the melting point of the PPS, another molded product 20 composed of a liquid crystal polymer (LCP), polyetheretherketone (PEEK), and the like is combined.

<4. Manufacturing method of composite molded product>

As described above, the composite molded product 1 uses the surface (surface 10a) on which the microgroove 12 is provided in the resin molded product 10 having the trenches as a contact surface, and another molded product 20 is disposed adjacent to the surface. The composite molded product 1 can be obtained by, for example, stack molding (insertion molding).

Hereinafter, a method for manufacturing the composite molded product 1 by stack molding 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 product is taken as an example.

(Manufacturing of composite molded products by stack mold forming)

FIG. 4 is a schematic diagram illustrating a method of obtaining a composite molded product 1 by stack mold forming. As shown in FIG. 4, a resin is first molded once to prepare a preform 10 ′ of a resin molded product 10 having a groove (FIG. 4 (1)).

Next, a part of the surface 10a 'of the preparation body 10' is partially removed from the resin, and a plurality of minute grooves 12 are formed on the surface 10a '(Fig. 4 (2)). Thereby, a resin molded article 10 having grooves is produced. At this time, in the present embodiment, the width W _{12 of the} plurality of micro-trenches 12 is formed according to the ratio of the width W ₁₃ of the ridge 13 between the micro-trenches 12 and the width W ₁₂ of the micro-trench 12 (W ₁₃ : W ₁₂ ) becomes a 1: 1.5 to 5 method, and a micro trench 12 is formed.

Next, as shown in FIG. 4 (3), a resin molded article 10 having a trench is loaded into a mold (not shown), and the surface 10a on which the micro trench 12 is provided is a contact surface inside the mold. The secondary resin [uncured material (melt) constituting the material of the other molded product 20] is flowed in, inserted (injected and injected), and cured.

Here, the secondary resin (melt) does not specifically limit the flow direction of the surface 10a of the resin-molded article having a gully, and it is preferable to conform to the tree having the gully. The longitudinal direction of the minute grooves 12 formed on the fat-molded product 10 flows in parallel. If the secondary resin is caused to flow in a direction orthogonal to the longitudinal direction of the micro-gully 12, the wall of the micro-gully 12 will easily collapse due to the flow of the secondary resin, and the possibility of the gully being buried will increase. On the other hand, by causing the secondary resin to flow in a direction parallel to the longitudinal direction of the micro-gully 12, the micro-gully 12 can be prevented from being melted and broken, and the secondary resin can flow into the micro-gully 12 more effectively. .

Through the above steps, a composite molded product 1 with a curable resin (another molded product 20) can be obtained by stack molding. In addition, similarly, by using a thermoplastic resin that is heated and melted by the secondary resin, a composite molded product 1 with a thermoplastic resin can be obtained by stack molding.

[Example]

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments. In addition, in the following examples and comparative examples, three types of samples were manufactured (for example, three types of samples such as Examples 1-1 to 1-3 were manufactured according to the conditions of Example 1), and the results were shown in Table 1 below. The breaking load (N) was measured as shown.

"Manufacturing of resin molded products and composite molded products with trenches"

[Example 1]

． Manufacturing of grooved resin molded products

Using glass fiber-doped PPS (DURAFIDE® PPS 1140A7, manufactured by Jusu Corporation) (melting point: about 280 ° C), injection molding was performed under the following conditions to obtain injection molded products (resin molded products, primary molded products).

(DURAFIDE® PPS injection molding conditions)

Pre-drying: 140 ° C, 3 hours

Extrusion temperature: 320 ℃

Mold temperature: 140 ° C

Injection speed: 20mm / sec

Holding pressure: 50MPa (500kg / cm ² )

With respect to the obtained resin molded article, a plurality of minute grooves were formed on the surface of the resin molded article by laser irradiation under the conditions shown in Table 1 below. In addition, the depth of the micro trench was set to 100 μm. Here, the "pitch" in Table 1 refers to the total value of the width of the gully portion of the minute gully on the surface of the resin molded product and the width of the ridge portion on one side adjacent to the gully 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 groove width of the micro-gully is W ₁₂ and the width of the ridge is W ₁₃ . The "micro-groove shape on the surface" refers to the micro-groove shape on the surface of the resin molded product, as shown in "horizontal lines" as shown in FIG. 3 (A) or as “oblique grids” as shown in FIG. 3 (B).

That is, in Example 1, a resin-molded article was formed with stripe-shaped micro-grooves of W ₁₃ : W ₁₂ = 40 μm: 160 μm (1: 4) at a pitch of 200 μm, thereby obtaining a resin-molded product having grooves.

The conditions of the laser irradiation treatment are as follows.

(Laser Irradiation Conditions at the Time of Formation of Micro Gully)

Oscillation wavelength: 1.064 μm

Maximum rated output: 13W (average)

Laser output: 45%

Scanning speed: 1000mm / sec

Frequency: 40kHz

Rewrite: 40 times

※ Draw 3 times at 30μm pitch

※ 230 ℃ × 3hr preheating

． Manufacturing of composite molded products

Next, with respect to the resin molded product (primary molded product) having the gully obtained as described above, the surface provided with the micro gully formed by laser irradiation is used as a contact surface, and the mold for injection molding is inserted, and another molding is performed. The material of the product (secondary molded product) was LCP (VECTRA® LCP E130i, manufactured by Jusu Corporation), and injection molding was performed under the following conditions to obtain a composite molded product.

(VECTRA® injection molding conditions)

Pre-drying: 140 ° C, 4 hours

Extrusion temperature (forming temperature): 380 ° C

Mold temperature: 60 ℃

Injection speed: 200mm / sec

Holding pressure: 50MPa (500kg / cm ² )

[Example 2]

In Example 2, a resin having grooves was produced in the same manner as in Example 1 except that the shape of the micro grooves on the surface of the resin molded article was a diagonal lattice shape during the production of the resin molded article having grooves. A molded article is then used to produce a composite molded article based on the obtained resin molded article having grooves.

[Example 3]

In Example 3, except when forming a resin molded article having grooves, a stripe-shaped minute groove W ₁₃ : W ₁₂ = 90 μm: 210 μm (1: 2.3) was formed at a pitch of 300 μm. Example 1 A resin-molded article having a groove was manufactured in the same manner, and a composite molded article was produced from the obtained resin-molded article having a groove.

[Example 4]

In Example 4, a resin with grooves was produced in the same manner as in Example 3, except that the shape of the micro grooves on the surface of the resin molded product was a diagonal lattice shape during the manufacture of the resin molded products with grooves. A molded article is then used to produce a composite molded article based on the obtained resin molded article having grooves.

[Comparative Example 1]

In Comparative Example 1, except for forming groove-shaped micro-grooves of W ₁₃ : W ₁₂ = 100 μm: 100 μm (1: 1) at a pitch of 200 μm during the manufacture of a resin molded article having a trench, the rest were implemented. Example 1 A resin-molded article having a groove was manufactured in the same manner, and a composite molded article was produced from the obtained resin-molded article having a groove.

[Comparative Example 2]

In Comparative Example 2, except for the formation of micro grooves in the shape of a diagonal grid of W ₁₃ : W ₁₂ = 100 μm: 100 μm (1: 1) during the manufacture of a resin molded product having grooves, the rest were implemented. Example 1 A resin-molded article having a groove was manufactured in the same manner, and a composite molded article was produced from the obtained resin-molded article having a groove.

"Evaluation"

<Enlarged observation of a resin-molded product having a trench>

Regarding the resin molded article (primary molded article) having a groove in Example 1 and Comparative Example 1, one surface provided with a minute groove was enlarged and observed with an electron microscope (SEM). FIG. 5 (A) is a SEM photograph of a resin-molded article having grooves produced in Example 1. FIG. FIG. 5 (B) is a SEM photograph of a resin-molded article having grooves produced in Comparative Example 1. FIG. The magnifications were each set to 200 times.

As can be seen from the SEM photograph of FIG. 5 (A), Example 1 is a resin molded article provided with minute grooves having a wide groove width (W ₁₃ : W ₁₂ = 1: 4). On the other hand, as shown in the SEM photograph of FIG. 5 (B), Comparative Example 1 is a resin molded article having a micro-trench with a width of 1: 1 of the trench and the ridge.

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

Regarding the composite molded product of Example 1 and Comparative Example 1, the resin molded product with a trench (primary molded product) when the secondary molded product (LCP) was peeled off and peeled off from the composite molded product was observed under an enlarged electron microscope (SEM). surface. Fig. 6 (A-1) (magnification 200 times) and Fig. 6 (A-2) (magnification 50 times) are resin moldings having grooves after tearing and peeling off the secondary molded product from the composite molded product 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 groove after tearing and peeling off the secondary molded article from the composite molded article of Comparative Example 1. FIG.

It is known from the SEM photographs of FIGS. 6 (A-1) and (A-2) that if the composite molded product of Example 1 is torn apart and peeled off from the secondary molded product, micro grooves are formed in the resin molded product having grooves. The stripe-like LCP shape similar to the shape of the micro-gully remains at the part. This phenomenon can be said to be that the molten material of the secondary molded product (LCP) effectively flows into the micro-gully of the resin-molded product having the gully, and the anchor effect caused by the glass fiber exposed in the micro-gully makes the second The secondary molded product is sufficiently bonded to a resin molded product having a groove.

On the other hand, from the SEM photograph of FIG. 6 (B), it was found that the composite molded product of Comparative Example 1 was peeled and the secondary molded product was peeled off. There was no LCP residue at the portion where the micro grooves were formed. Part of the surface of the resin molded product remaining on the non-gully part. In other words, this composite molded product is said to be insufficiently bonded. This phenomenon can be considered to be performed by injection molding the LCP which has a molding temperature higher than the melting point of the resin PPS constituting the resin molded product having grooves. During molding, minute grooves of a resin molded product having grooves are melted and damaged, and as a result, there is no molten material flowing into the LCP in the grooves. In addition, the composite molded article of Comparative Example 1 can be peeled off very easily with the hand of the tester when the secondary molded article is peeled off (see the results of the breaking load (N) described later).

<Enlarged cross-section observation of a composite molded product>

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

From the cross-sectional photo of FIG. 7 (A), it is known that the composite molded product of Example 1 has a micro-ditch formed inside a resin-molded product (primary-molded product) having a trench, and some of it has actually entered the secondary molded product. LCP. On the other hand, from the cross-sectional photo of FIG. 7 (B), it was found that the composite molded product of Comparative Example 1 had micro-groove melting damage during the molding of the secondary molded product, and the primary molded product (PPS) and the secondary molded product. (LCP) is in contact with the horizontal plane. That is, it was found that before the LCP entered the micro trench formed on the PPS, the micro trench was melted and damaged.

In addition, FIG. 8 shows another cross-sectional photograph of the composite molded product of Comparative Example 1 observed with an optical microscope. As can be seen from the cross-sectional photo of FIG. 8, the composite molded product of Comparative Example 1 was formed on the surface of a resin molded product having grooves along with the LCP flow (in the flow direction indicated by the arrow) belonging to the secondary molded product. The walls of the micro-gully will melt and collapse, and the micro-gully is blocked. In addition, it was learned that as the melting of the tiny trenches progressed, PPS and LCP would appear doped and mixed. Together. In this case, as shown in FIG. 7 (B), a sufficient amount of LCP is not entered in the micro-trench.

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

In order to evaluate the joint strength (joint strength of the primary molded product and the secondary molded product) of the composite molded products obtained in the examples and comparative examples, such a breaking load (tensile breaking load) (N) was measured. The joint strength was measured based on the breaking load. The measuring machine used a tensile machine UTA-50kN (manufactured by ORIENTEC), and the composite molded product (120 mm in length, 20 mm in width, and 2 mm in thickness) was peeled and peeled at a chuck speed of 1 mm / min. The measurement results of the breaking load (N) and the micro-groove formation conditions of the resin molded product having the grooves are shown in Table 1 below.

In addition, as described above, in the examples and comparative examples, three types of samples were produced in each of the relevant examples (for example, the conditions of Example 1 are three types of samples such as Examples 1-1 to 1-3), and the results are shown in Table 1 below. The breaking load (N) was measured.

From the results shown in Table 1, it was found that the composite molded products of Examples 1 to 4 had an average breaking load of 125 N or more, and confirmed that they had sufficient bonding strength. Among them, in Example 2 and Example 4 in which the micro-gully was formed into a diagonal grid, the failure modes of all the samples were not peeling failure, but the failure of the base material, and it was found that higher bonding strength can be obtained.

On the other hand, the trench width of the micro-gully did not widen W ₁₃ : W ₁₂ = 1: Comparative Examples 1 and 2, regardless of the shape of the micro-gully is striped or grid-like, the breaking load is about 30 ~ Around 40N, it is a very low joint strength. This phenomenon can be considered as shown in Fig. 7 (B) and Fig. 8, because the forming temperature at the time of the inflow of LCP, which is a secondary molded product, is higher than the melting point of PPS, so before the inflow of LCP, the tiny grooves were melted and damaged. There is no reason for LCP to enter. Therefore, the anchor effect caused by the glass fiber cannot be fully utilized, and it is judged that a low bonding strength is exhibited.

10‧‧‧Resin molded article with groove

10a‧‧‧ surface

11‧‧‧ inorganic filler

12‧‧‧Mini Gully

12a‧‧‧ sidewall

13‧‧‧ridge

W ₁₂ 、 W ₁₃ ‧‧‧Width

D‧‧‧ Depth

Claims (4)

A method for manufacturing a composite molded product, which is arranged on the surface of a first resin molded product containing an inorganic filler, and adjacently arranges a second molded product composed of a resin having a molding temperature higher than the melting point of the first resin molded product, and A method for manufacturing a composite molded product forming a composite molded product includes a groove forming step, which includes a plurality of ridges on a surface of the first resin molded product adjacent to the second molded product and located between the minute grooves. And the gully portion of the micro-gully are formed on the surface so that the width of the surface becomes a ratio of 1: 1.5 to 5 to form the micro-gully in which the inorganic filler protrudes from the side wall; and the forming step is to form the micro-gully On the surface of the first resin molded product, a melt of the second molded product constituent material flows into the surface of the first resin molded product, and is solidified to be molded. The method for manufacturing a composite molded article according to item 1 of the scope of the patent application, wherein the above-mentioned forming step uses one surface having the above-mentioned minute grooves as a contact surface, flows into the above-mentioned second molded article constituent material, and is cured by injection molding And forming steps. The method for manufacturing a composite molded article according to item 1 or 2 of the scope of patent application, wherein the inorganic filler is a fibrous inorganic filler. The method for manufacturing a composite molded article as described in item 1 or 2 of the scope of the patent application, wherein the gully forming step is a step of forming a micro gully by laser irradiation.