JPWO2017199992A1 - Composite molded article and manufacturing method thereof - Google Patents

Abstract

Even when a material having a low tensile strength is used for another molded product, it is possible to sufficiently bond one resin molded product and another molded product made of a material having a low tensile strength. The composite molded product according to the present invention includes an inorganic filler 11 and has a grooved resin molded product 10 in which a groove 12 in which the inorganic filler 11 is exposed is formed, and a groove 11 of the grooved resin molded product 10. And another molded article 20 disposed adjacent to the surface. There are a plurality of grooves 11, and the ratio of the groove area A12 to the total of the groove area A12 formed by the grooves 11 and the peak area A13 formed by the peaks 13 located between the grooves 12 is in the range of 75% to 97%. Is in. The other molded product 20 is made of a material having a melting point lower than that of the resin constituting the resin molded product and a tensile strength of 50% or less of the tensile strength of the resin.

Description

  The present invention relates to a composite molded article and a method for producing the same.

  In recent years, in areas such as automobiles, electrical products, industrial equipment, etc., there has been an increasing movement to replace some metal molded products with resin molded products in order to meet demands for reducing carbon dioxide emissions and manufacturing costs. ing. Accordingly, composite molded products in which a resin molded product and a metal molded product are integrated are widely used. Moreover, the present invention is not limited to this, and composite molded products in which molded products made of the same or different materials are integrated are widely used.

  As a manufacturing method of a composite molded product in which one molded product and another molded product are integrated, for example, the following is proposed. That is, in Patent Document 1, a resin such as glass fiber is mixed with a resin constituting one molded product, and a resin, a plasma, a flame, or the like is bonded to the surface to which the resin constituting the other molded product is bonded. Processed to a thickness of 0. A method has been proposed in which after removing a resin of several μm to several tens of μm, the other resin is in contact with a surface to which the other resin is bonded, and the resin is filled, molded, and bonded. Further, in Patent Document 2, a surface of one resin molded product is irradiated with electromagnetic radiation to form a nanostructure on the surface, and then the other resin molded product is contacted with the surface and filled and molded. A method of integrating them has been proposed.

  In addition, Patent Document 3 discloses that a minute groove is formed on the surface of a resin molded product (primary resin molded product) containing an inorganic filler to expose the inorganic filler, and a secondary molded product is formed in the minute groove. In the method of manufacturing a composite molded product with improved strength by pouring the constituent materials into one, and Patent Document 4, the melting point of the material constituting the secondary molded product constitutes the primary resin molded product When the melting point of the resin is higher than the melting point of the resin, the ratio of the width of the crest located between the microgrooves to the width of the microgrooves is 1: 1.5 to 5 (the groove width is crested). There is also proposed a method of forming a plurality thereof so that the width is wider than the width of the portion.

JP-A-01-126339 JP 2011-529404 A International Publication No. 2014/125999 International Publication No. 2015/033728

  However, depending on the combination of the materials of one molded product and another molded product, there is room for further improvement with respect to strength when joined. For example, if a groove is formed on the surface of one molded product and the melting point of the material constituting the other molded product is lower than the melting point of the material constituting the one molded product, the other molded product is configured. When a material (for example, an elastomer) whose tensile strength is significantly lower than the material constituting one molded product is used as the material to be used, the strength at the joint of another molded product is insufficient depending on the shape of the groove. For reasons, it may not be possible to join with high strength.

  The present invention has been made in view of the above-described situation. For example, even when a material having low tensile strength is used for another molded product, the resin molded product and the material having low tensile strength are used. An object of the present invention is to sufficiently bond the other molded product.

  The inventors of the present invention have made extensive studies in order to solve the above-described problems. As a result, with respect to one resin molded product, a part of the resin of the resin molded product containing the inorganic filler is removed, and a plurality of grooves in which the inorganic filler is exposed are formed on the surface of the resin molded product. It has been found that the surface area of the molded product is formed such that the ratio of the area of the groove occupying the region composed of the plurality of grooves and the peaks located between the plurality of grooves is within a specific range. Thus, the other molded product joined to the grooved resin molded product is made of a material having a melting point lower than that of the resin constituting the one resin molded product and a tensile strength of 50% or less of the tensile strength of the resin. Even in this case, it was found that high bonding strength can be achieved, and the present invention has been completed. That is, the present invention provides the following.

  (1) The present invention contains an inorganic filler and is adjacent to a grooved resin molded product in which a groove in which the inorganic filler is exposed is formed, and a surface of the grooved resin molded product having the groove. A ratio of the groove area to a total of a groove area formed by the grooves and a mountain area formed by a mountain located between the grooves. Is in the range of 75% to 97%, the other molded product has a lower melting point than the resin constituting the resin molded product, and the tensile strength is 50% or less of the tensile strength of the resin. It is a composite molded article made of a certain material.

  (2) Moreover, this invention is a composite molded product with which the said inorganic filler protrudes from the side wall of the said groove | channel, and is exposed in the resin molded product with a groove | channel of invention of (1).

  (3) Moreover, this invention is a composite molded product by which the said groove | channel is formed in the grid | lattice form in the said surface of the resin molded product with a groove | channel of invention of (1) or (2).

  (4) Further, the present invention is a composite molded article according to any one of (1) to (3), wherein the inorganic filler is a fibrous inorganic filler.

  (5) Moreover, this invention is a composite molded product in which the said groove | channel is formed by laser irradiation in any invention of (1) thru | or (4).

  (6) Further, the present invention is a composite molded product according to any one of (1) to (5), wherein the material constituting the other molded product is an elastomer.

  (7) Moreover, this invention is a composite molded article whose said elastomer is ethylene ethyl acrylate in invention of (6).

  (8) Further, the present invention provides a resin having a melting point lower than that of the resin constituting the first resin molded product on the surface of the first resin molded product containing an inorganic filler and having a tensile strength. A method for producing a composite molded product in which a second molded product made of a material having a tensile strength of 50% or less is disposed adjacently to form a composite molded product, wherein the first resin molded product and the second resin molded product A plurality of grooves in which the inorganic filler protrudes from the side wall thereof on the surface adjacent to the molded article, and the total of the groove area formed by the grooves and the mountain area formed by the peaks located between the grooves on the surface A groove forming step for forming a ratio of the groove area to 75% or more and 97% or less on the surface of the first resin molded product on which the groove is formed; A molding step of pouring and solidifying a melt of the material constituting the molded article of A method for producing a composite molded article having a.

  According to the present invention, for example, the other molded article is made of a material having a melting point lower than that of the resin constituting one resin molded article and significantly lower tensile strength than the resin constituting one resin molded article. Even if it is a case, one resin molded product and other molded products can fully be joined.

It is the figure which showed typically the expanded cross section of the composite molded product of this embodiment. It is the figure which showed typically the expanded cross section of the resin molded product with a groove | channel which is a component of a composite molded product. It is an electron microscope (SEM) photograph of the resin molded product with a groove | channel which formed the grid | lattice-like groove | channel on the surface, (A) is the groove area which a groove | channel makes, and the mountain area which the mountain located between grooves makes. It is a photograph (corresponding to Example 3) when the ratio of the groove area to the total is 91%, and (B) is a photograph (corresponding to Example 4) when the ratio is 96%. It is a figure for demonstrating the process when obtaining a composite molded product by multiple shaping | molding (insert molding). 1 is a schematic diagram of a grooved resin molded product manufactured in Example 1. FIG. (A) is a SEM photograph of the grooved resin molded product produced in Example 1, and (B) is a SEM photograph of the grooved resin molded product produced in Comparative Example 2. 6 is a SEM photograph of a fracture surface of a grooved resin molded product produced in Example 5. FIG.

  Hereinafter, a specific embodiment of the present invention (hereinafter referred to as “the present embodiment”) will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment, A various change is possible in the range which does not change the summary of this invention.

<1. Composite molded products>
FIG. 1 is a schematic diagram of an enlarged cross section of a composite molded article 1 according to the present embodiment. As shown in FIG. 1, the composite molded product 1 includes a grooved resin molded product 10 and another molded product 20.

[Resin molded product with groove]
FIG. 2 is a view schematically showing a cross section of the grooved resin molded product 10 (also simply referred to as “resin molded product”). The grooved resin molded product 10 contains an inorganic filler 11, and a plurality of grooves 12 (also simply referred to as “grooves”) from which the inorganic filler 11 is exposed are formed on the surface 10 a of the grooved resin molded product 10. ing.

And in this resin molded product 10 with a groove | channel, the groove | channel 12 makes | forms in the area | region on the surface 10a which consists of the several groove | channel 12 formed in the surface 10a, and the peak 13 located between the several groove | channel 12. The ratio (A ₁₂ / (A ₁₂ + A ₁₃ )) of the groove area A ₁₂ to the sum of the groove area A ₁₂ and the peak area A ₁₃ formed by the peaks 13 is 75% or more and 97% or less. It is characterized by.

  In addition, although mentioned later in detail, the composite molded product 1 is formed by welding the other molded product 20 by using the surface 10a of the resin molded product 10 in which the some groove | channel 12 was formed as a contact surface.

[resin]
The type of resin is not particularly limited as long as the groove 12 can be formed by a resin removing means such as laser irradiation or chemical treatment. For example, polyphenylene sulfide (PPS), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), polyacetal (POM) and the like can be exemplified as those capable of forming grooves by laser irradiation.

  Examples of the chemical treatment include decomposition treatment with an acid or alkali, dissolution treatment with a solvent, and the like. In the case of an amorphous thermoplastic resin, it is easy to dissolve in various solvents, but in the case of a crystalline resin, both solvents are selected and used. For example, polybutylene terephthalate (PBT), polyacetal (POM), etc. can be mentioned as those that can form grooves by adding acid or alkali. Here, in the chemical treatment, it is important to perform a chemical treatment limited to a portion where a groove is formed, and to remove a product by the chemical treatment.

  In addition, as resin, thermoplasticity may be sufficient and thermosetting may be sufficient.

[Inorganic filler]
The inorganic filler 11 is not particularly limited as long as it is exposed to the groove 12 by removing a part of the resin constituting the grooved resin molded product 10 to form the groove 12. The inorganic filler 11 is exposed from the side wall 12a of the formed groove 12 into the space (in the groove) of the groove 12, and the grooved resin molded product 10 and the other molded product 20 are combined with the composite molded product 1 and When it does, it plays the role of the anchor which suppresses those separation (refer FIG. 2). Further, by exposing the inorganic filler 11 to the groove 12 in this way, the inorganic filler 11 itself can be prevented from falling off from the composite molded article 1.

  Although it does not specifically limit as the inorganic filler 11, Glass fiber, carbon fiber, whisker fiber, glass flake, mica etc. can be mentioned.

  Moreover, it is preferable that the length of the inorganic filler 11 is longer than the length of the groove 12 in the short direction (width direction in the cross-sectional view of FIG. 1). In other words, the length of the groove 12 in the short direction is preferably shorter than the length of the inorganic filler 11 in the long direction. For example, if the shape is fibrous, the average fiber length is preferably longer than the length of the groove 12 in the short direction. If the shape is irregular, plate-like, or particulate, the long diameter, preferably the average particle diameter. Is preferably longer than the length of the groove 12 in the short direction.

  In the present embodiment, the inorganic filler 11 exposed in the groove 12 serves as an anchor that suppresses the separation of the joint between the grooved resin molded product 10 and the other molded product 20 as described above. Is. Therefore, in order to fulfill this role, for example, the crests 13 formed by removing a part of the resin between the laser irradiation part and the non-irradiation part are bridged by the inorganic filler 11 exposed in the groove 12. (Bridge) is preferable. And it is preferable that the shape of the inorganic filler 11 is a fibrous form by the point which can be bridge | crossed by the inorganic filler 11 in this way. In the unevenness formed in the resin, the concave portion is the groove 12, and the convex portion sandwiched between the plurality of grooves 12 is the mountain 13.

  Although content of the inorganic filler 11 is not specifically limited, It is preferable that it is the range of 5 to 80 weight part with respect to 100 weight part of resin. If the content is less than 5 parts by weight, even if the inorganic filler 11 is exposed in the groove 12, it may not be able to fulfill the role of an anchor that suppresses the destruction of the grooved resin molded product 10 and other molded products 20. There is. On the other hand, if the content exceeds 80 parts by weight, the grooved resin molded product 10 may not have sufficient strength.

[Preferable commercial product of resin material containing inorganic filler 11]
In addition, as a resin material containing the inorganic filler 11, PPS with glass fiber (product name: DURAFIDE (registered trademark) PPS 1140A64, manufactured by Polyplastics Co., Ltd.), PPS with glass fiber / inorganic filler (product name: DURAFIDE) (Registered trademark) PPS 6165A7, manufactured by Polyplastics Co., Ltd.), LCP with glass fiber (product name: Laperos (registered trademark) LCP E130i, manufactured by Polyplastics Co., Ltd.), and the like are commercially available.

[groove]
A plurality of grooves 12 are formed on the surface 10a of the resin molded product 10, and the inorganic filler 11 is exposed from the side wall (side surface) 12a. The groove 12 is formed by removing a part of the resin constituting the resin molded product 10, and thus removing a part of the resin so that the inorganic filler 11 protrudes from the side wall 12a. Can be exposed.

  In addition, as shown in FIG. 1, when the surface (surface 10a) which has the groove | channel 12 of this grooved resin molded product 10 is made into a contact surface and integrated with the other molded products 20, the composite molded product 1 is manufactured. In the composite molded article 1, the inorganic filler 11 is not exposed. In the present specification, even when the inorganic filler 11 is not exposed in the composite molded product 1, the inorganic filler 11 is exposed from the groove 12 in a mode in which the other molded product 20 is removed from the composite molded product 1. If so, “the inorganic filler 11 is exposed in the groove 12”.

  The longitudinal direction of the groove 12 (the direction toward the back side in the sectional view of FIG. 2) is preferably different from the longitudinal direction of the inorganic filler 11. When the longitudinal direction of the groove 12 and the longitudinal direction of the inorganic filler 11 are the same, for example, the uneven portions 13 formed by removing a part of the resin by the laser irradiation site and the non-irradiation site. There is a possibility that the inorganic filler 11 cannot be suitably placed between them. Then, the inorganic filler 11 is likely to drop off from the grooved resin molded product 10, and there is a possibility that the role of an anchor that suppresses the breakage of the grooved resin molded product 10 and other molded products 20 cannot be sufficiently achieved. Therefore, as shown in the cross-sectional view of FIG. 2, it is preferable to form the groove 12 by performing laser irradiation or the like on the resin so that the longitudinal direction of the groove 12 is different from the longitudinal direction of the inorganic filler 11.

  By the way, in one resin molded product with a groove in which a groove is formed (referred to as “one resin molded product 50” for convenience of explanation), the surface on which the groove (referred to as “groove 51” for convenience of explanation) is formed. On the other hand, a composite molded product (referred to as “composite molded product 70” for convenience) is manufactured by welding and integrating other molded products (referred to as “other molded product 60” for convenience). At this time, as a material constituting the other molded product 60, a material (for example, an elastomer) having a significantly lower tensile strength than that of the resin constituting the resin molded product 50 may be used. In such a case, the strength of the other molded product 60 is obtained at the joint portion of the composite molded product obtained by melting (filling) the other molded product 60 into one grooved resin molded product 50. There may be a shortage. If it becomes like this, the inorganic filler will be exposed to the groove | channel 51, the melt of the material which comprises the other molded product 60 will be filled into the groove | channel 51, and the one resin molded product 50 and the other molded product 60 will be filled. Even if they are bonded together, the strength of the bonded portion cannot be obtained sufficiently.

Therefore, in the present embodiment, in the groove 12 formed in the grooved resin molded product 10, the ratio of the groove 12 in the surface 10a of the grooved resin molded product 10 is controlled within a predetermined range. Specifically, in the region on the surface 10a composed of the peaks 13 positioned between the plurality of grooves 12, the groove area A12 formed by the grooves ₁₂ and the total peak area A13 formed by the peaks ₁₃ occupy the total. The area of the groove 12 is made large so that the ratio of the groove area A ₁₂ (A ₁₂ / (A ₁₂ + A ₁₃ )) is 75% or more and 97% or less.

Here, the groove area A ₁₂ and the mountain area A ₁₃ refer to the area on the surface 10a of the grooved resin molded product 10, and the area (groove area) A ₁₂ of the groove ₁₂ is as indicated by a dotted line X in FIG. It refers to the area of the groove on the surface of the opening of the groove 12 that is on the extension (surface) of the surface (surface 10a) of the peak 13.

FIG. 3A shows an electron micrograph of the grooved resin molded product 10 in which the groove 12 is formed on the surface 10a. As shown in FIG. 3A, in the grooved resin molded product 10, the area of the groove 12 (groove area) is widened, and the ratio represented by A ₁₂ / (A ₁₂ + A ₁₃ ) is 75% or more and 97 % Or less. In the grooved resin molded product 10, the groove area of the groove 12 is thus increased, so that the other molded product 20 has a lower melting point than the resin constituting the grooved resin molded product and has a tensile strength of the resin. Even if it is a case where it consists of a material (for example, elastomer) which is 50% or less of the tensile strength of, the intensity | strength in the junction part of the said other molded article 20 is securable. Thereby, the resin molded product 10 with a groove | channel and the other molded product 20 can be firmly stuck (joined).

To give a specific example, in the surface 10a of the resin molded product 10, each of the grooves 12 and the crests 13 is one set (pitch), and the grooves 12 are formed in a lattice shape with the same vertical and horizontal pitches. pitch 200 [mu] m, it may be 100μm both the width _{W 13} of width _{W 12} and mountain 13 of the groove 12 (in this _case, the _{a 12 / (a 12 + a} 13) = 75%.). Further, at a pitch of 200 μm, for example, the width W _{13 of the} peak 13 can be set to 50 μm and the width W _{12 of the} groove 12 can be set to 150 μm (in this case, approximately A ₁₂ / (A ₁₂ + A ₁₃ ) = 94. %.)

Further, when one pitch between the groove 12 and the crest 13 is 300 μm, for example, the width W _{12 of the} groove 12 and the width W 13 of the crest ₁₃ can both be 150 μm (in this case, A ₁₂ / (A ₁₂ + A ₁₃ ) = 75%). Further, at a pitch of 300 μm, the width W ₁₃ of the crest 13 can be set to 100 μm and the width W _{12 of the} groove 12 can be set to 200 μm (in this case, approximately A ₁₂ / (A ₁₂ + A ₁₃ ) = 89%) Become.).

Note that these specific examples are merely examples and are not limited thereto. If A ₁₂ / (A ₁₂ + A ₁₃ ) is in the range of 75% to 97%, the groove 12 and the mountain 13 It can be appropriately determined according to the size of the pitch.

Regard the area _{A 12} of the grooves 12 in the surface 10a of the grooved resin molded article 10, the area _{A 12} of the groove 12 relative to the sum of the area _{A 13} of the area _{A 12} and mountain 13 of the groove 12 is less than 75% In addition, the strength of the joint portion of the other molded product 20 (the portion filled in the groove portion of the grooved resin molded product 10 in the other molded product 20) becomes insufficient, and an external force is applied to the composite molded product 1, There is a possibility that the joint portion of the other molded product 20 is broken. On the other hand, when the area _{A 12} of the groove 12 is more than 97% of the total of the area _{A 13} of the area _{A 12} and mountain 13 of the groove 12, the inorganic filler 11 contained in the grooved resin molded product 10, The portion exposed from the grooved resin molded product 10 is increased, and the inorganic filler 11 is easily removed from the grooved resin molded product 10, whereby the role of the anchor is not sufficiently fulfilled, and external force is applied to the composite molded product 1. Therefore, there is a possibility that the joint portion of the composite molded product 1 is likely to be broken.

Regarding the area _{A 12} of the groove 12, is to define a _{"A 12 / (A 12 + A} 13) " area _{A 12} of the groove 12 so that 78 to 95% in the proportions represented by, more preferably It is particularly preferable that the content be 85 to 93%. Thereby, while improving the intensity | strength of the other molded product 20 in a junction part, drop-off | omission of the inorganic filler 11 in the molded product 10 with a groove | channel is suppressed, and it can be set as the resin molded product 10 with high joint strength.

  Here, the groove | channel 12 may be formed in the grid | lattice form as shown in FIG. 3 in the surface 10a of the resin molded product 10, and may be formed in stripe form. When the grooves 12 are formed in a lattice shape, the grooves 12 can be formed in an oblique lattice shape in which the longitudinal direction of the grooves 12 is different from the longitudinal direction of the inorganic filler 11. As shown in FIG. 3, by forming the grooves 12 in a lattice shape, the melt of the material constituting the other molded product 20 can be poured more reliably into the grooves 12.

When forming the grooves 12 in a lattice shape, the area A ₁₃ of the area A ₁₂ and mountain 13 of the groove 12 at the surface 10a, in the region surrounded by the groove of the outermost of the plurality of grooves 12 to form a grating shape When the total area of the plurality of grooves 12 and the plurality of peaks 13 in the region is viewed, the area of the grooves 12 and the peaks 13 is A ₁₂ / (A ₁₂ + A ₁₃ ) of 75% or more 97 % As long as the relationship is satisfied.

In addition, when the groove 12 and the crest 13 have an area of A ₁₂ / (A ₁₂ + A ₁₃ ) = 75% or more and 97% or less when the groove 12 is formed in a lattice shape in this way, one of the grooves 12 The ratio of the widths of the plurality of grooves 12 and the plurality of peaks 13 in the longitudinal direction (x-axis) and the other longitudinal direction (y-axis) may be the same or different.

The depth D of the groove 12 is preferably not less than ½ of the length in the short direction of the groove 12 (that is, the width W _{12 of the} groove ₁₂ ). When the depth D is less than ½ of the width W ₁₂ of the groove 12, the inorganic filler 11 exposed to the groove 12 and the other fillers are formed when the composite molded article 1 is formed by bonding with the other molded article 20. There is a possibility that a sufficient anchor effect does not occur between the molded product 20 and the grooved resin molded product 10 and the other molded product 20 cannot be firmly brought into close contact with each other.

[Method for producing grooved resin molded product]
In the grooved resin molded product 10, a resin molded product containing the inorganic filler 11 is subjected to laser irradiation, chemical treatment, or the like to partially remove the resin, and a plurality of grooves 12 are formed on the surface 10 a of the resin molded product. It is obtained by doing. In the grooved resin molded article 10, the surface 10 a of the resin molded article is partially removed in this way to form the groove 12, whereby the inorganic filler 11 contained in the resin molded article is removed from the side wall 12 a of the groove 12. Exposed from.

The laser irradiation is set based on the type of material to be irradiated, the output of the laser device, and the like. However, if the groove 12 is not formed by irradiating the resin with appropriate energy, the inorganic filler 11 is sufficiently exposed. It may be difficult to form a groove 12 having a width W ₁₂ or a depth D as set.

In the present embodiment, when forming the grooves 12, the surface 10a of the grooved resin molded article 10, the area A ₁₂ of the groove, relative to the total of the peaks of the area A ₁₃ that is located between the grooves, the grooves The ratio of the area A ₁₂ of (A ₁₂ / (A ₁₂ + A ₁₃ )) is 75% or more and 97% or less.

In the present embodiment, by forming the groove 12 to widen the area A ₁₂ in this manner, other molded article 20 is, with respect to the tensile strength of the resin constituting the grooved resin molded article, less than 50% Even when it is made of an elastomer having a tensile strength of 1, it is possible to increase the strength of the other molded product 20 at the joint portion of the composite molded product 1. Thereby, the other molded product 20 can be sufficiently joined to the resin molded product 10.

  Here, when forming the groove 12 by laser irradiation, the glass fiber or the like as the inorganic filler 11 partially shields the energy of the laser. Therefore, in order to remove the resin deeply, if laser irradiation is performed a plurality of times, it is necessary to give higher energy by the amount of energy absorbed when the laser hits an already exposed glass fiber or the like later. Therefore, when laser irradiation is repeated a plurality of times, it is preferable to include a step of increasing the laser irradiation amount from the previous irradiation amount.

  Further, in order to remove the resin located on the back surface of the inorganic filler 11 having low laser light transmittance, it is preferable to perform laser irradiation from a direction other than perpendicular to the surface 10 a of the resin molded product 10.

  On the other hand, in forming the groove 12 by chemical treatment, an acid, an alkali, an organic solvent, or the like corresponding to the characteristics of the resin is selected and used. In a polyacetal resin molded product in which the resin is decomposed by an acid, the groove can be formed by decomposing and removing the position where the groove is provided with an acid. Further, in the case of an amorphous resin molded product that is easily dissolved in an organic solvent, the groove can be formed by previously removing the portion other than the location where the groove is provided on the surface of the molded product and then dissolving and removing the organic solvent.

[Other molded products]
Returning to FIG. As shown in FIG. 1, in the composite molded product 1, the surface (surface 10 a) having the groove 12 of the resin molded product 10 with groove is used as a contact surface, and another molded product 20 is disposed adjacent to the surface. Yes.

  Here, as the other molded product 20, the melting point is lower than the resin constituting the grooved resin molded product 10, and the tensile strength is 50% or less of the tensile strength of the resin constituting the grooved resin molded product 10 (for example, 30% or less) is used. The “tensile strength” in the present invention is measured in accordance with ISO527-1,2.

In the present embodiment, the material constituting the other molded article 20 has a lower melting point than the resin constituting the grooved resin molded article 10 and the tensile strength of the resin constituting the grooved resin molded article 10. Even when a material that is 50% or less is used, the strength of the other molded product 20 at the joint can be increased. In other words, taking a wide area _{A 12} of the plurality of grooves 12 formed in the grooved resin molded article 10, _A 12 _/ in relation to the area _{A 13} of the mountain 13 located between the grooves 12 (A 12 _{+ A 13)} By satisfying 75% or more and 97% or less, the grooved resin molded product 10 and the other molded product 20 can be effectively joined.

  For example, as a combination of the material of the grooved resin molded product 10 and another molded product 20, the resin constituting the grooved resin molded product 10 is polyphenylene sulfide having a melting point of about 280 ° C. and a tensile strength of about 200 MPa (as a specific example, polyplastic In the case of DURAFIDE (registered trademark) PPS 1140A64, etc., manufactured by SU Some polybutylene terephthalate, polyacetal which is a material of 200 ° C. or lower, or various elastomers (mostly melting point 150 ° C. or lower, 120 ° C. or lower) contain no reinforcing material such as glass fiber or a small amount. Not present (such materials typically have a tensile strength of 100 MPa or less (grooves For example, 50% or less of the tensile strength of the resin constituting the attached molded article 10). Among materials that can be used for other molded products 20, some elastomers, amorphous resins, and thermosetting resins do not have a value corresponding to a specific “melting point” measured by DSC measurement or the like. (It may be expressed in terms of softening point, flowable temperature, etc.) In such a material, the processing temperature (cylinder temperature, curing temperature, etc.) when molding other molded products can be regarded as the melting point in the present invention.

<2. Manufacturing method of composite molded product>
As described above, the composite molded product 1 has the surface (surface 10a) having the groove 12 of the resin molded product 10 with grooves as a contact surface, and another molded product 20 is disposed adjacent to the surface. This composite molded product 1 can be obtained by, for example, multiple molding (insert molding).

  Hereinafter, a method for producing the composite molded product 1 by multiple molding will be described in detail. Here, a case where a thermoplastic elastomer is used as a material constituting another molded product is taken as an example.

[Manufacture of composite molded products by multiple molding]
FIG. 4 is a schematic diagram for explaining a method of obtaining the composite molded article 1 by multiple molding. As shown in FIG. 4, first, the primary resin is primary molded to produce a preliminary body 10 ′ of the grooved resin molded product 10 (FIG. 4 (1)).

Subsequently, the resin is partially removed from a part of the surface 10a ′ of the preliminary body 10 ′, and a plurality of grooves 12 are formed on the surface 10a ′ (FIG. 4B). Thereby, the resin molded product 10 with a groove | channel is produced. At this time, in the present embodiment, the area AW ₁₂ of a plurality of grooves 12 formed is, a percentage of the total of the area A ₁₃ of the mountain 13 which become located between the groove 12 (A ₁₂ / The groove 12 is formed so as to be 75% or more and 97% or less as (A ₁₂ + A ₁₃ ).

  Subsequently, as shown in FIG. 4 (3), the grooved resin molded product 10 is put into a mold (not shown), and a secondary surface is formed using the surface 10a having the groove 12 as a contact surface inside the mold. The material (melt of thermoplastic elastomer constituting the other molded article 20) is poured and cooled to solidify it.

  Here, the flow direction of the secondary material (melt) with respect to the surface 10a of the grooved resin molded product is not particularly limited, but in the longitudinal direction of the groove 12 formed in the grooved resin molded product 10. It is preferable to make it flow so that it may become parallel. When the secondary material is caused to flow in a direction orthogonal to the longitudinal direction of the groove 12, the wall of the groove 12 may fall down due to the pressure when the secondary material flows, and the groove may be destroyed. On the other hand, by causing the secondary material to flow in a direction perpendicular to the longitudinal direction of the groove 12, the destruction of the groove 12 can be suppressed and the secondary material can be poured into the groove 12 more effectively. it can.

  By passing through the above processes, the composite molded product 1 with the thermoplastic elastomer (other molded products 20) can be obtained by multiple molding. Similarly, by using the secondary material as an uncured thermosetting elastomer, a composite molded product 1 with a thermosetting elastomer by multiple molding can be obtained.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following examples and comparative examples, for each example, a sample of a grooved resin molded product was manufactured at the area ratio shown in Table 1 below, and then a composite of the grooved resin molded product and another molded product was manufactured. The molded product was manufactured, and the joint strength (MPa) of the composite molded product was measured.

<Manufacture of composite molded products>
[Example 1]
[Manufacture of resin molded products with grooves]
Glass-filled PPS (Durafide (registered trademark) PPS 1140A64, manufactured by Polyplastics Co., Ltd.) (melting point: about 280 ° C., tensile strength: 200 MPa) is injection-molded under the following conditions to produce an injection-molded product (resin-molded product) , Primary molded product).
(Conditions for injection molding in primary molded products)
Pre-drying: 140 ° C, 3 hours Cylinder temperature: 320 ° C
Mold temperature: 140 ° C
Injection speed: 20mm / sec
Holding pressure: 50 MPa (500 kg / cm ² )

With respect to the obtained resin molded product, a plurality of grooves were formed on the surface of the resin molded product by laser irradiation under the conditions shown in Table 1 below. The depth of the groove was 100 μm. Here, in Table 1, “pitch” refers to a value obtained by combining the width of the groove on the surface of the resin molded product and the width of the peak on one side adjacent to the groove. In addition, “A ₁₂ / (A ₁₂ + A ₁₃ )” is the groove portion occupying the sum of the areas of the peak portion (convex portion) and the groove portion (concave portion) when the groove portion area A ₁₂ and the peak portion area A ₁₃ are used. It is the ratio of area A ₁₂ width. Further, the “groove shape on the surface” is a shape of the groove on the surface of the resin molded product, and indicates “horizontal stripes” or “lattice shape” as shown in FIG.

That is, in Example 1, a lattice-shaped groove having A ₁₂ / (A ₁₂ + A ₁₃ ) of 75% is formed at a pitch of 200 μm with respect to a resin molded product, and thereby a grooved resin molded product is formed. Obtained.

The conditions for the laser irradiation treatment were as follows.
(Conditions for laser irradiation in groove formation)
Oscillation wavelength: 1.064 μm
Maximum rated output: 13W (average)
Laser output: 45%
Scanning speed: 1000mm / sec
Frequency: 40kHz
Overwriting: 40 times

[Manufacture of composite molded products]
Next, with respect to the grooved resin molded product (primary molded product) obtained as described above, the surface having the groove formed by laser irradiation is used as a contact surface and inserted into an injection mold. As a material related to a molded product (secondary molded product), the melting point is lower than that of the resin constituting the grooved resin molded product (specifically, 100 ° C. or less), and the tensile strength is the resin constituting the grooved resin molded product. Injection under the following conditions using ethylene ethyl acrylate (NUC-6570, manufactured by NUC Corporation, melting point: about 91 ° C., tensile strength: 7 MPa) which is 50% or less (specifically, 10% or less) of the tensile strength. Molded to obtain a composite molded product.
(Conditions for injection molding in secondary molded products)
Pre-drying: None Cylinder temperature (molding temperature): 220 ° C
Mold temperature: Approx. 30 ° C (cooling at room temperature)
Injection speed: 10mm / sec
Holding pressure: 20 MPa

[Example 2]
Example 2 was the same as Example 1 except that in the production of a resin-molded product with grooves, lattice-like grooves with A ₁₂ / (A ₁₂ + A ₁₃ ) = 89% were formed at a pitch of 300 μm. A grooved resin molded product was manufactured, and a composite molded product was manufactured based on the obtained grooved resin molded product.

Example 3
Example 3 was the same as Example 1 except that in the production of a grooved resin molded product, lattice-shaped grooves with A ₁₂ / (A ₁₂ + A ₁₃ ) = 91% were formed at a pitch of 200 μm. A grooved resin molded product was manufactured, and a composite molded product was manufactured based on the obtained grooved resin molded product.

Example 4
Example 4 was the same as Example 3 except that in the production of a grooved resin molded product, lattice-like grooves with A ₁₂ / (A ₁₂ + A ₁₃ ) = 96% were formed at a pitch of 300 μm. A grooved resin molded product was manufactured, and a composite molded product was manufactured based on the obtained grooved resin molded product.

[Comparative Example 1]
In Comparative Example 1, in the production of a grooved resin molded product, the same procedure as in Example 1 was performed except that lattice-shaped grooves with A ₁₂ / (A ₁₂ + A ₁₃ ) = 56% were formed at a pitch of 300 μm. A grooved resin molded product was manufactured, and a composite molded product was manufactured based on the obtained grooved resin molded product.

[Comparative Example 2]
In Comparative Example 2, a grooved resin molded product was produced in the same manner as in Example 1 except that a lattice-shaped groove with A ₁₂ / (A ₁₂ + A ₁₃ ) = 72% was formed at a pitch of 300 μm. A grooved resin molded product was manufactured, and a composite molded product was manufactured based on the obtained grooved resin molded product.

<Evaluation>
[Enlarged observation of resin molded products with grooves]
About the resin molded product with a groove | channel (primary molded product) which concerns on Example 1 and the comparative example 2, the surface which has a groove | channel was enlarged and observed with the electron microscope (SEM). 6A is an SEM photograph of the grooved resin molded product produced in Example 1. FIG. 6B is an SEM photograph of the grooved resin molded product produced in Comparative Example 2. FIG. The magnification was 200 times.

As can be seen from the SEM photograph of FIG. 6A, in Example 1, a resin molded product having a large groove area (A ₁₂ / (A ₁₂ + A ₁₃ ) = 75%) was obtained. On the other hand, as shown in the SEM photograph of FIG. 6B, in Comparative Example 2, a resin molded product having a narrow groove area (A ₁₂ / (A ₁₂ + A ₁₃ ) = 72%) was used.

[Joint strength]
In order to evaluate the joint strength (joint strength between the primary molded product and the secondary molded product) of the composite molded products obtained in Examples and Comparative Examples, their tensile fracture strength (MPa) was measured. For measuring the bonding strength, Tensilon UTA-50kN (Orientec Co., Ltd.) is used as a measuring instrument, the crosshead speed is 1 mm / min, and the composite molded product (120 mm length, 20 mm width, 2 mm thickness) is pulled off. I went there. Table 1 below shows the measurement results of the bonding strength (MPa) together with the groove forming conditions of the grooved resin molded product.

  Samples were produced for each of the examples and comparative examples, and the bonding strength (MPa) was measured for each as shown in Table 1 below.

  As can be seen from the results shown in Table 1, in the composite molded articles according to Examples 1 to 4, it was confirmed that the bonding strength was 3 MPa or more, and that the bonding strength was sufficient. Among them, in Example 3 where the ratio of the groove area was 91%, it was found that higher bonding strength was obtained.

  On the other hand, in Comparative Examples 1 and 2 in which the groove area was not widened and the ratio of the groove area was less than 75%, the bonding strength was as low as less than about 3 MPa. This is considered to be because the strength of the other molded product (secondary molded product) at the joint portion of the composite molded product is low. As a result, it is considered that the other molded product applied to the joint portion is easily broken and has a low joint strength.

  Moreover, as Example 5, the plasticizer and the crosslinking agent were kneaded into the resin molded product with groove (primary molded product) obtained in the same manner as in Example 1 as another molded product (secondary molded product). Using a composite molded product obtained by compression molding of nitrile butadiene rubber (tensile strength 20 MPa) with a mold at 160 ° C., the fracture surface was observed after the joints were pulled apart. As shown in FIG. It was confirmed that the rubber that had entered the base material was destroyed and a good bonding state was obtained.

DESCRIPTION OF SYMBOLS 1 Composite molded product 10 Grooved resin molded product 10a Surface of grooved resin molded product 11 Inorganic filler 12 Groove 12a Groove side wall 13 Pile 20 Other molded products

Claims (8)

A grooved resin molded article containing an inorganic filler, wherein a groove in which the inorganic filler is exposed is formed;
Another molded article disposed adjacent to the surface having the groove of the grooved resin molded article,
The groove is plural,
The ratio of the groove area to the total of the groove area formed by the grooves and the mountain area formed by the peaks located between the grooves is in the range of 75% to 97%,
The other molded article is a composite molded article made of a material having a melting point lower than that of the resin constituting the resin molded article and a tensile strength of 50% or less of the tensile strength of the resin.   The composite molded article according to claim 1, wherein the inorganic filler protrudes from a side wall of the groove and is exposed.   The composite molded article according to claim 1 or 2, wherein the grooves are formed in a lattice shape on the surface.   The composite molded article according to any one of claims 1 to 3, wherein the inorganic filler is a fibrous inorganic filler.   The composite molded article according to claim 1, wherein the groove is formed by laser irradiation.   The composite molded article according to any one of claims 1 to 5, wherein the elastomer is an olefin-based elastomer.   The composite molded article according to claim 6, wherein the olefin-based elastomer is ethylene ethyl acrylate. On the surface of the first resin molded product containing an inorganic filler, the melting point is lower than that of the resin constituting the first resin molded product, and the tensile strength is 50% or less of the tensile strength of the resin. A method for producing a composite molded product in which a second molded product made of a material is arranged adjacently to form a composite molded product,
The surface of the first resin molded product adjacent to the second molded product has a plurality of grooves from which the inorganic filler protrudes from the side wall, and the groove area formed by the grooves on the surface is between the grooves. A groove forming step of forming the ratio of the groove area to the total of the mountain area formed by the mountains located in the range of 75% or more and 97% or less;
Manufacturing of a composite molded article having a molding step of pouring and solidifying a melt of the material constituting the second molded article on the surface of the first resin molded article in which the groove is formed Method.