JP2019089297A - Composite member and method for producing the same - Google Patents

Abstract

To provide a composite member in which resins or a resin and a dissimilar material are made into a composite, and a new method for producing the same.SOLUTION: There is provided a composite member in which a first member having a layer formed of inorganic particles and a second member formed of a resin having a shrinkage ratio sh (%) and an elastic modulus E (MPa) satisfying a relationship of E≤10,000×exp (-2.64×sh) are joined to each other on a base material. In the composite member, the second member is formed of a resin composition having a shrinkage ratio sh (%) and an elastic modulus E (MPa) satisfying a relationship of E≤63,000×exp (-2.64×sh).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite member in which resins, or resins and different materials are joined, and a method of manufacturing the same.

  Composite members in which resins or resin and dissimilar materials such as metal, glass, and inorganic materials are joined have been conventionally used in automobile interior members such as a console box around an instrument panel, engine interior parts, interior parts, digital cameras They are used in parts that come in contact with the outside world, such as the housing of electronic devices such as mobile phones and the like, interface connections, and power supply terminals.

  As a method of compounding resin and resin or resin and different material, a method of forming minute unevenness on the joint surface of the other member to be joined with the resin and joining by the anchor effect, adhesive agent, double-sided tape Bonding methods using different materials and / or resin molded products, and fixing members such as folded pieces and claws, using the fixing members to fix them together, and bonding using screws, etc. . Among these, the method of forming minute irregularities on a resin plate or a metal plate and the method of using an adhesive are effective in terms of the degree of freedom in designing a composite molded product (Patent Documents 1 and 2).

International Publication No. WO 2014/125999 Brochure JP, 2014-117724, A

In the methods described in Patent Documents 1 and 2 described above, since a groove is formed on the surface of the target member by a laser, there is local heat generation, which may cause deformation due to thermal expansion of the bonding member. In addition, when laser processing is performed on a resin, there is a problem that carbides of the resin may remain on the bonding surface to deteriorate the bonding property over time.
An object of the present invention is to provide a composite member in which resins are mixed or resins and different kinds of materials such as metal, glass, and inorganic materials, and a new manufacturing method thereof.

The present invention is achieved by the following.
1. Consisting of a first member having a layer consisting of inorganic particles on a base material, and a resin composition in which the shrinkage factor sh (%) and elastic modulus E (MPa) satisfy E ≦ 100000 × exp (−2.64 × sh) And a second member.
2. The composite member according to the above 1, wherein the second member is made of a resin composition in which the shrinkage ratio sh (%) and the elastic modulus E (MPa) satisfy E ≦ 63000 × exp (−2.64 × sh) .
3. The composite member according to the above 1 or 2, wherein the resin composition contains an elastomer.
4. The composite member formed by joining the 1st member which has a layer which consists of inorganic particles on a base material, and the 2nd member which consists of a resin composition containing an elastomer.
5. The composite member according to 3 or 4, wherein the elastomer is at least one selected from an olefin polymer, a polyester elastomer, a urethane elastomer, and an acrylic polymer.
6. The composite member according to any one of 3 to 5, wherein the elastomer is an elastomer containing a glycidyl group.
7. The composite member according to any one of the above 1 to 6, wherein the layer made of the inorganic particles is made of inorganic particles having an average particle diameter of 1 to 500 nm.
8. The composite member according to any one of 1 to 7, wherein the layer made of the inorganic particles has a thickness of 1 to 1,500 nm.
9. The composite member according to any one of 1 to 8, wherein the layer composed of the inorganic particles is composed of a close-packed inorganic particle.
10. The composite member according to any one of the above 1 to 9, wherein the base material has a surface roughness measured according to JIS B 0601: 1982, Rz = Rmax ± 10%, and Rmax = 1 to 10 μm.
11. 11. The composite member according to any one of 1 to 10, wherein the layer on the substrate substantially consists of only the inorganic particles.
12. The composite member according to any one of 1 to 11, wherein the resin composition contains 5 to 50% by mass of a filler composed of inorganic particles having a particle diameter of 0.1 to 50 μm.
13. The composite member according to any one of 1 to 12, wherein the substrate is made of at least one selected from resin, glass, ceramic and metal.
14. The composite member according to any one of 1 to 13, wherein the thermal conductivity λ (W / m · k) of the substrate is 2.0 or less.
15. In the method for producing a composite member according to any one of 1 to 14, the first member is formed by forming a layer composed of inorganic particles on a substrate by an advection accumulation method, and on the first member, The manufacturing method of the composite member which joins by injection molding the 2nd member which consists of a resin composition with which shrinkage | contraction rate sh (%) and elastic modulus E (MPa) satisfy | fill E <= 100000xexp (-2.64xsh).

  In the composite member of the present invention, the base material is not deformed by heat, and even when the base material is a resin, the ashing property does not remain, and the bonding property over time can be secured.

It is a top view which shows typically embodiment 1 of the composite member of this invention. FIG. 2 is a perspective view of a composite member embodiment 1; It is a schematic diagram of the method to evaluate the joint strength of composite member embodiment 1. FIG. It is a schematic diagram which shows the sample form for an airtightness test. It is a longitudinal cross-sectional view which shows the method of airtightness evaluation using an airtightness tester. It is a perspective view of the 1st member (A) and composite member (B) of Embodiment 3 of this invention.

  Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.

<Composite member>
One aspect of the composite member of the present invention is a first member having a layer comprising inorganic particles on a substrate, and a shrinkage rate sh (%) and an elastic modulus E (MPa) of E ≦ 10000 × exp (−2.64) It is characterized by joining with the 2nd member which consists of a resin composition which fills xsh). Moreover, another aspect of the composite member of the present invention is formed by bonding a first member having a layer comprising inorganic particles on a substrate and a second member comprising a resin composition containing a thermoplastic resin and an elastomer. It is characterized by

«First member having a layer consisting of inorganic particles on a substrate»
The layer composed of inorganic particles on the first member of the present invention (hereinafter, also simply referred to as a particle layer) is preferably composed of inorganic particles having an average particle diameter of 1 to 500 nm. Moreover, it is preferable that the thickness of a layer is 1-1500 nm. This layer is preferably a layer consisting of closely packed inorganic particles. Specifically, for example, a layer in which inorganic particles are arranged by using a so-called advection accumulation method is preferable.

  The particle layer by this method is known to accumulate particles by lateral capillary force to form a close-packed structure. The present invention is characterized in that this particle layer is used to bond two members. That is, the present invention provides a composite member according to an unprecedented bonding method in which an inorganic particle layer having a close-packed structure formed on a substrate serves as a bonding material.

  Note that in order to make the inorganic particles uniformly dispersed on the bonding surface of the first member, the inorganic particles are in a plurality of layers rather than in a state in which the inorganic particles are two-dimensionally arrayed (present only in one layer) on the surface of the first member. It is preferable that the inorganic particle layer is extremely thick, but in the case where the inorganic particle layer is extremely thick, the inorganic particles are three-dimensionally laminated several times in the thickness direction in the layer, and thus inorganic Since there is a risk that a decrease in bonding strength between the first member and the second member may occur due to peeling from the boundaries between the particles, the inorganic particle layer is formed such that the inorganic particles are uniformly distributed over the entire bonding surface of the first member. It is preferable to be in a state of being arranged dimensionally (5 layers or less, for example, 1 to 3 layers).

  As inorganic particles, usual inorganic particles such as silica particles, titanium particles and alumina particles, metal particles and metal oxide particles can be applied. The average particle size is preferably 1 to 500 nm, more preferably 10 to 100 nm, and still more preferably 20 to 50 nm. The thickness of the layer made of inorganic particles is preferably 1 to 1500 nm, more preferably 10 to 300 nm, and still more preferably 20 to 100 nm.

  It is preferable that the layer which consists of inorganic particles of this invention is close packing. When the inorganic particles are all spherical of the same size, the volume packing ratio at close packing is theoretically about 74%, but in practice the shapes of the inorganic particles usually vary to some extent. Moreover, even when inorganic particles are stacked in the thickness direction, when considering bonding with the second member, it is considered that the influence of the filling state of the inorganic particles in the outermost layer is large, so The closest packing means that the area filling ratio of the inorganic particles in the outermost layer of the layer made of inorganic particles is 80% or more, and more preferably 85% or more.

  The average particle diameter of the inorganic particles and the thickness of the layer formed of the inorganic particles were measured by a transmission electron microscope (TEM). Specifically, on the image of the surface of the inorganic particle layer formed on the substrate taken by TEM, the diameters of ten randomly extracted inorganic particles are measured to obtain the average particle diameter, On the image which image | photographed the cross section of the particle layer by TEM, the average value which measured the thickness of the layer in five places of random was made into the thickness of the layer which consists of inorganic particles.

  Moreover, it was determined by observing the arbitrary area | region (1 micrometer x 1 micrometer) in the inorganic particle layer formation surface of a base material by TEM, and observing the filling state of the inorganic particle in outermost layer whether it is closest packing. Here, in the case where the inorganic particles are stacked in the thickness direction in the observation region, and the stacked state is not uniform, the area filling rate averaged by appropriately performing image processing may be obtained.

«Base material»
The base material for forming the particle layer of the present invention is not limited as long as it is a base material made of a material to which the advection accumulation method can be applied. For example, metal, glass, ceramic, resin, etc. may be mentioned, but in order to form a close-packed structure with stronger bonding power uniformly, the material has a thermal conductivity of 10 W / m · K or less for the base material. Is preferable, a material of 5 W / m · K or less is more preferable, and a material of 2.0 W / m · K or less is even more preferable.

  It is presumed that this is preferable in order to achieve closer packing because particle self-accumulation phenomena proceed gently. In addition, if the thermal conductivity of the substrate is low, the volatilization of the liquid phase in which the inorganic particles are dispersed also proceeds gently, and it is presumed that the particle layer is likely to be uniformly formed over the entire surface. The thermal conductivity is the thermal diffusivity by the laser flash method, the specific heat by DSC, the specific gravity by the water displacement method (based on the JIS Z 8807 solid specific gravity measurement method), and [thermal conductivity] = [thermal diffusivity × Specific heat × specific gravity] was calculated.

  As a resin, usual cyclic polyolefin (COC), polyacetal (POM), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyetheretherketone (PEEK), liquid crystalline resin (LCP), etc. Is a preferable thermoplastic resin, and in particular, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyphenylene sulfide (PPS), and liquid crystalline resin (LCP) are preferably used. The thermal conductivity of these resins is 1.0 W / m · K or less.

  Examples of the ceramic include alumina, zirconia and silicon nitride. Their thermal conductivity is 0.5 to 1.5 W / m · K. Examples of the metal include aluminum, stainless steel, magnesium, copper, titanium and the like. Their thermal conductivity is 10 to 400 W / m · K.

<< Base material whose surface roughness is Rz = Rmax ± 10% and Rmax = 1 to 10 μm >>
The surface of the substrate on which the particle layer of the present invention is formed preferably has a surface roughness of Rz = Rmax ± 10% and Rmax = 1 to 10 μm. More preferable Rz is Rmax ± 5%. Further, Rmax is more preferably 1.5 to 8 μm, further preferably 2 to 5 μm. By making such surface roughness, the filling property of the inorganic particles can be improved.

  In order to obtain such surface roughness, when producing a substrate, using a mold suitable for the required surface roughness, polishing the substrate surface after production, plasma the substrate surface Treatment with an active species such as ultraviolet light, corona discharge, etc., or physical and / or chemical formation and / or removal of irregularities on the substrate surface, and inclusion of particles that cause the substrate to produce irregularities It can be adjusted by etc.

  The surface roughness of the present invention is in accordance with JIS B 0601: 1982, using a contact-type surface roughness measuring device (Mitsutoyo Co., Ltd., contour shape measuring device surf test SV-3000 CNC), the central portion of the flat test piece The range of 15 mm perpendicular to the flow direction of the

«Second member made of a resin composition in which the shrinkage ratio sh (%) and the elastic modulus E (MPa) satisfy E 10000 10000 x exp (-2.64 x sh) >>
The second member of the present invention is a resin composition in which the shrinkage ratio sh (%) and the elastic modulus E (MPa) satisfy the relationship of E ≦ 10000 × exp (−2.64 × sh). As such a resin composition, the resin mentioned by the 1st member can be used.

  Olefin resin composition, acrylic resin composition, polyester resin composition, polyacetal resin composition, PPS resin composition, etc. as a resin composition containing an inorganic filler, an elastomer, etc. in addition to the preferable resin mentioned in the first member Is also mentioned as a preferable resin as the second member. Examples of the inorganic filler include glass fibers, glass beads, glass flakes, talc, mica, silica and other fibrous, plate-like, granular and powdery inorganic fillers, and in particular, an inorganic particle layer formed on the first member When the inorganic filler of the same quality as that of the inorganic material to be used is contained, it is preferable in that the affinity between the inorganic particle layer of the first member and the second member is excellent.

  Moreover, as a particle size, it is preferable to include an inorganic filler of 0.1 to 50 μm, and it is preferable to include one having an aspect ratio of 1 to 3 of the inorganic filler. As for content of an inorganic filler, it is preferable that the resin composition which comprises a 2nd member contains 5-50 mass% of the above-mentioned inorganic fillers. Preferred elastomers include olefin polymers such as ethylene-ethyl acrylate copolymer (for example, NUC-6570 manufactured by NUC Co., Ltd.), and polyester polymers, urethane elastomers, acrylic polymers of polymethacrylic acid esters. (For example, Zefac manufactured by Aika Kogyo Co., Ltd., staphyroid, etc.) and the like can be mentioned.

These elastomers may be used as copolymers, or in the form of core-shell particles, as long as they can be mixed with the composition of the present invention.
A glycidyl group-containing elastomer is also preferable as the elastomer, and a glycidyl group-containing olefin copolymer such as ethylene-glycidyl methacrylate copolymer or ethylene-glycidyl methacrylate-methyl acrylate copolymer is preferable as the glycidyl group-containing elastomer (For example, Sumitomo Chemical Co., Ltd. product bond first) is mentioned.

  As content of an elastomer, it is preferable to contain 1-30 mass% in the resin composition which comprises a 2nd member, and when an elastomer is an elastomer containing a glycidyl group, content of a glycidyl group is 2nd It is preferable that it is 0.01-1 mass% in the resin composition which comprises a member.

  These elastomers may be used as a resin composition constituting the second member in a state of being contained as an additive in the above-mentioned resin, or the elastomer itself or an elastomer may contain an additive such as an inorganic filler. May be used as a resin composition that constitutes the second member.

  In the present invention, the reason why the second member made of the resin composition having the above-mentioned characteristics exerts a strong bonding force is estimated as follows. The particle layer on the first member is first exerted by forming an adhesive force with the substrate so as to have a close-packed structure by the advective accumulation method. The resin composition having a shrinkage factor and an elastic modulus satisfying the above equation is excellent in the followability to the surface shape of the close-packed particle layer, and the surface area of the close-packed structure is observed to be strong as a result. .

  In the present invention, “shrinkage rate sh (%)” means a mold having a side gate of 4 mm in width × 2 mm in thickness provided with a flat test piece of 80 mm × 80 mm × 2 mm at the center of one side. The molding shrinkage ratio in the direction perpendicular to the flow when the resin composition constituting the second member is injection molded under the same molding conditions as the molding conditions of the second member in actual production of the composite member ( After molding, using a flat test piece left to stand at 23 ° C. and 50% RH for 24 hours or more, the dimension in the flow perpendicular direction of the molded product at a position of 20 mm from the end on the non-gate side (side of flow end) (The width of a flat test piece) is measured, and the difference (the amount of shrinkage) from the die size corresponding to the position is divided by the die size, which means "elastic modulus E (MPa)" , Refers to the flexural modulus measured according to ISO 178.

<Method of manufacturing composite member>
«Method of manufacturing first member»
In the present invention, the inorganic particles constituting the layer on the surface of the substrate may be water, isopropyl alcohol, methanol, ethylene glycol, propylene glycol, ethylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dimethylacetamide, acetic acid The substrate is immersed in a liquid dispersed in a liquid phase such as ethyl, toluene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like, and pulled up, thereby forming an inorganic particle layer on the surface of the substrate by the so-called advection accumulation method One member can be manufactured.

  The medium used for the liquid phase preferably has a viscosity of 0.1 to 100 mPa · s at 25 ° C., preferably 0.5 to 50 mPa · s, from the viewpoint of the ease of arrangement of the inorganic particles at the time of formation of the inorganic particle layer. And more preferably 1 to 30 mPa · s. The content of the inorganic particles in the medium is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.

  However, as long as it is possible to form a layer in which inorganic particles are densely arranged on the surface of a substrate, it is not limited to the advection accumulation method, and various thin film forming methods such as coating by brush or spray, spin coating, etc. may be used. You can also. Here, when the inorganic particle layer is formed, the coated liquid is wiped off or masking is applied to the substrate in advance, if necessary, depending on the requirements such as the design property, except for the portion used for bonding with the second member. By setting, the inorganic particle layer may not be provided.

  In the present invention, a liquid in which inorganic particles are dispersed is disposed on the surface of a substrate, and then the liquid is dried and volatilized to produce a first member in which a layer substantially consisting of only inorganic particles is formed. Can. Here, in order to form a layer in which the inorganic particles are uniformly arranged, it is desirable to allow the drying and volatilization of the liquid to proceed uniformly, and from that viewpoint, the medium of the liquid phase has a boiling point of 50 to 200 ° C. Is preferable, the thing of 60-160 degreeC is more preferable, and the thing of 70-130 degreeC is further more preferable.

  When a resin is used as the base material, a resin molded product to be the base material may be produced by a commonly used method such as injection molding or extrusion molding, and if it is glass similarly, a float method, down draw method, ceramic etc. If it is, what was manufactured by the method used normally, such as a normal-pressure sintering method and reaction sintering method, can be used. These base materials may be appropriately processed such as cutting and welding according to requirements for designability, functionality, fixation with other members, and the like.

«Method of bonding the second member»
In the present invention, the resin composition constituting the second member is brought into contact with the inorganic particle layer of the first member in a molten state, and then the resin composition is cooled and solidified to join the second member. I do. The bonding method is not particularly limited. For example, the first member having an inorganic particle layer is disposed in a mold for molding a second member, and the resin composition constituting the second member is an inorganic particle of the first member. The second member can be joined by injection molding (so-called insert molding) on the layer, or a state in which a region used for joining among the surfaces of the second member formed in advance is heated and melted. The bonding can also be performed by bringing a pressure (so-called welding) into contact with the inorganic particle layer of the first member.

  The conditions for insert molding and welding of the second member are not particularly limited, and can be appropriately set according to the type of resin contained in the resin composition constituting the second member. In addition, if it is insert molding, since formation of a 2nd member and joining with a 1st member can be performed simultaneously, it is advantageous in the surface of process simplification. In addition, when the rigidity and toughness of the first member are low and the first member is deformed or damaged by resin pressure in insert molding, if bonding is performed by welding, the degree of freedom in setting of the pressurizing condition is high. This is advantageous because it is easy to suppress the deformation and breakage of the first member.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, evaluation was performed in a measurement room of 23 ° C. and 50% RH unless otherwise specified.

[Evaluation of joint strength]
<Preparation of base material>
Aluminum: Nippon Light Metal Co., Ltd. “A5052” (thermal conductivity 138 W / m · K) is cut to 45 mm × 18 mm × 1.5 mm so that the 45 mm × 18 mm single side has the surface roughness shown in Table 1 Polished.

<Production of First Member (Formation of Particle Layer)>
The substrate is immersed in a liquid containing 15% by mass of silica fine particles having a particle size of 25 nm in isopropyl alcohol, and then pulled up once such that the polishing surface is perpendicular to the liquid surface. Silica fine particles were applied to the polished surface of the material by the advective flow accumulation method, dried at 23 ° C. to volatilize isopropyl alcohol, and an inorganic particle layer was formed on the surface of the substrate to produce a first member. TEM observation of an arbitrary region (1 μm × 1 μm) of the inorganic particle layer formation surface revealed that the area filling rate of the silica fine particles was about 90%, and they were arranged in the closest packed state.

<Manufacture of composite member (joining with second member)>
Inside of a mold for molding a composite member, designed to overlap a part of the inorganic particle layer forming surface of the first member and a part of an 80 mm × 10 mm × 4 mm cavity for forming the second member Then, the first member was installed, and the composite member as shown in FIGS. 1 and 2 was manufactured by insert molding by injection molding the resin composition constituting the second member. Here, for the first member and the second member, in the inorganic particle layer forming surface of the first member, a region having a width of 10 mm at the center of the short side (18 mm) × 10 mm from the short side end is It arrange | positions so that the area | region of the edge part 10 mm x 10 mm of a 2nd member may be overlapped. The combination of the first member and the second member is as shown in Table 1, and the respective resin compositions used for the second member and the molding conditions thereof are as follows.

  POM resin composition 1: Polyplastics Co., Ltd. polyacetal resin composition "Duracon (registered trademark) M 90-44" (shrinkage ratio 2.0%, elastic modulus 2500 MPa), cylinder temperature 200 ° C, mold temperature 80 ° C, The injection molding was carried out at an injection speed of 20 mm / sec and a holding pressure of 60 MPa.

  POM resin composition 2: 50% by mass of polyacetal resin composition "Duracon (registered trademark) M140-44" manufactured by Polyplastics Co., Ltd. and 50 mass% of polyester-based elastomer "Grelax E510N" manufactured by Toyobo Specialties Trading Co., Ltd. % And a polyacetal resin composition (shrinkage ratio 1.3%, elastic modulus 800 MPa) melt-kneaded, and injection molded at a cylinder temperature of 200 ° C., a mold temperature of 80 ° C., an injection speed of 15 mm / sec and a holding pressure of 60 MPa.

POM resin composition 3: 74% by mass of polyacetal resin composition "Duracon (registered trademark) M90-44" manufactured by Polyplastics Co., Ltd., and 24% by mass of core-shell polymer "Staphyloid PO-098" manufactured by Aika Kogyo Co., Ltd. And a polyacetal resin composition (shrinkage ratio 1.7%, elastic modulus 1100 MPa) obtained by melt-kneading 2% by mass of NUC Corporation ethylene-ethyl acrylate copolymer “NUC-6570” (cylinder shrinkage 200 ° C., gold) It was injection molded at a mold temperature of 80 ° C., an injection speed of 20 mm / sec, and a holding pressure of 60 MPa.

  POM resin composition 4: Polyplastics Co., Ltd. polyacetal resin composition "Duracon (registered trademark) M 270-44" at 53% by mass, Polyplastics Co., Ltd. polyacetal resin composition "Duracon (registered trademark) M 90- Polyacetal resin composition (shrinkage ratio 1.6%, elastic modulus 1000MPa) obtained by melt-kneading 10% by mass of 44 "and 37% by mass of urethane resin" Milactolan P485 RSUI "manufactured by Tosoh Corp. cylinder temperature 200 ° C, gold It was injection molded at a mold temperature of 80 ° C., an injection speed of 20 mm / sec, and a holding pressure of 60 MPa.

PBT resin composition: Polybutylene terephthalate resin composition "Duranex (registered trademark) 7507 K" (Wind shrink: 0.6%, elastic modulus: 13000 MPa) manufactured by Wintech Polymer Co., cylinder temperature 260 ° C., mold temperature 60 ° C. The injection molding was carried out at an injection speed of 20 mm / sec and a holding pressure of 60 MPa.

PPS resin composition 1: 59 mass% of polyphenylene sulfide resin “Fortron KPS” (melt viscosity at a temperature of 310 ° C. and a shear rate of 1216 sec− ¹ : 30 Pa · s) manufactured by Kureha Co., Ltd. Glass fiber manufactured by Nippon Electric Glass Co., Ltd. Melt-knead 35% by mass of “ECS 03 T-747” (average fiber length: 3 mm, average diameter: 13 μm) and 6% by mass of ethylene-glycidyl methacrylate copolymer “bond first 7L” manufactured by Sumitomo Chemical Co., Ltd. as elast. The obtained polyphenylene sulfide resin composition (shrinkage ratio 0.5%, elastic modulus 10000 MPa) was injection molded at a cylinder temperature of 320 ° C., a mold temperature of 150 ° C., an injection speed of 20 mm / sec and a holding pressure of 60 MPa.

  PPS resin composition 2: Polyplastics Co., Ltd. polyphenylene sulfide resin "Durafido (registered trademark) 0220A9" (shrinkage ratio 1.7%, elastic modulus 3800 MPa), cylinder temperature 320 ° C, mold temperature 150 ° C, injection speed It was injection molded at 15 mm / sec and a holding pressure of 60 MPa.

  PPS resin composition 3: Polyplastics Co., Ltd. polyphenylene sulfide resin "Durafido (registered trademark) 6165A6" (shrinkage rate 0.3%, elastic modulus 18300 MPa), cylinder temperature 320 ° C, mold temperature 150 ° C, injection speed It was injection molded at 20 mm / sec and a holding pressure of 60 MPa.

  COC resin composition: Polyplastics Co., Ltd. cyclic polyolefin resin "Topus (registered trademark) 6013S-04" (shrinkage ratio 0.2%, elastic modulus 2900 MPa), cylinder temperature 260 ° C, mold temperature 60 ° C, injection speed The injection molding was performed at 10 mm / sec and a holding pressure of 40 MPa.

  EEA resin composition: ethylene ethyl acrylate resin "NUC-6570" (shrinkage 3%, elastic modulus 20 MPa) manufactured by NUC Co., Ltd., cylinder temperature 250 ° C., mold temperature 30 ° C., injection speed 8 mm / sec, The injection molding was carried out under a holding pressure of 20 MPa.

<Evaluation of joint strength>
In the combination of the first member and the second member shown in Table 1, the burrs around the contact surface between the first member and the second member are first removed from the composite member adjusted by the above-described method, as shown in FIG. As shown, the first member was fixed to the recess of the test piece fixing jig 4. Next, using Tensilon UTA-50KN made by ORIENTEC Co., Ltd., the pressing jig 3 is lowered at a speed of 1 mm / min to push down the second member to separate the first member and the second member. The strength (MPa) was measured, and when the breaking strength was 10 MPa or more, the bonding strength was evaluated as ○, and when less than 10 MPa, as x. The results are shown in Table 1.

[Evaluation of air tightness]
<Preparation of Base Material and Production of First Member (Formation of Particle Layer)>
Aluminum: Japan Light Metal Co., Ltd. “A5052” (thermal conductivity 138 W / m · K) is cut into an annular plate with an outer diameter of 50 mmφ, an inner diameter of 20 mmφ, and a thickness of 1 mm. After polishing so as to be as described above, an inorganic particle layer was formed on the polished surface of the base by the same operation as the production of the first member in the evaluation of bonding strength, to obtain the first member 1.

<Manufacture of composite member (joining with second member)>
Part of the inorganic particle layer formation surface of the first member 1 and part of the cavity of 30 mmφ × 3 mm (the overlapping part with the first member is 2 mm thick) for forming the second member 2 overlap As shown in FIG. 4, the first member 1 is placed in a mold for molding a composite member designed to have the same structure, and the resin composition constituting the second member 2 is injection-molded on the inner diameter H. The composite member 5 was manufactured by insert molding. (A) is a plan view, (b) is a front view, and (c) is a cross-sectional view showing an AA cross section.

  Here, in the inorganic particle layer forming surface of the first member 1, the first member 1 and the second member 2 have an area of 5 mm in width from the inner diameter (20 mmφ), 5 mm in width × thickness from the end of the second member 2 It is arranged to overlap with the area of 2 mm. The molding conditions of the combination of the first member 1 and the second member 2 and the molding conditions of the respective resin compositions used for the second member 2 are as shown in Table 1 similarly to the above-mentioned evaluation of the bonding strength.

<Tightness evaluation>
In the combination of the first member 1 and the second member 2 shown in Table 1, first, after removing the burr around the contact surface between the first member 1 and the second member 2 for the composite member adjusted by the above method The following airtightness evaluation was performed using the apparatus shown in FIG.

  FIG. 5 is a longitudinal sectional view showing a method of air tightness evaluation using the air tightness tester 7. The airtightness tester 7 includes an airtightness tester body 8 and an airtightness tester lid 9. The composite member 5 was attached to the airtightness tester body 8 via the O-ring 10, and the lower portion of the composite member 5 was sealed. Thereafter, the airtight tester lid 9 was placed on the first member 1 of the composite member 5 and clamped.

  Then, distilled water 11 was poured onto composite member 5, and composite member 5 was completely immersed in distilled water 11. Air is fed through the line 12 and a pressure P of 0.1 MPa is applied to the inside of the airtightness tester body 13 for 6 minutes, and it is visually observed whether air bubbles leak from the interface between the first member 1 and the second member 2 Observed. The above test was carried out three times, and the evaluation results of air tightness according to the following criteria are shown in Table 1.

○: It was evaluated that the air tightness was good when no air bubble leakage was observed even once.
B: When air bubble leakage was confirmed 1 to 2 times, the air tightness was evaluated as moderate.
X: When leak was confirmed 3 times, it evaluated that airtightness was inferior.

なお、気密性はかなり厳しい評価であり、接合だけが必要な部材としては必ずしも必須の特性ではない。

In addition, air tightness is a quite severe evaluation, and it is not necessarily an essential characteristic as a member which requires only joining.

[Affected evaluation of inorganic filler type of second member]
The influence of the inorganic filler species of the second member was evaluated in the same manner as in the above-described evaluation of the bonding strength, except that the material constituting the second member and the molding conditions thereof were changed to the following. The results are shown in Table 2.

  LCP resin composition 1: Liquid crystal polymer composition containing 50% by mass of silica particles in liquid crystal polymer "Laperos (registered trademark) A950" manufactured by Polyplastics Co., Ltd. (shrinkage ratio 0.5%, elastic modulus 9500 MPa), cylinder temperature Injection molding was performed at 290 ° C., a mold temperature of 80 ° C., an injection speed of 100 mm / sec, and a holding pressure of 60 MPa.

  LCP resin composition 2: Liquid crystal polymer composition containing 50% by mass of glass beads in liquid crystal polymer "Laperos (registered trademark) A950" manufactured by Polyplastics Co., Ltd. (shrinkage ratio 0.5%, elastic modulus 9400 MPa), cylinder temperature Injection molding was performed at 290 ° C., a mold temperature of 80 ° C., an injection speed of 100 mm / sec, and a holding pressure of 60 MPa.

[Affected evaluation of substrate type and surface roughness]
<Preparation of base material>
a. Aluminum: Japan Light Metal Co., Ltd. “A5052” (thermal conductivity 138 W / m · K) is cut to 45 mm × 18 mm × 1.5 mm so that 45 mm × 18 mm single-sided surface roughness shown in Table 3 Polished.
b. Glass: Asahi Glass Co., Ltd. “Dragontrail” (thermal conductivity 0.65 W / m · K) is cut to 45 mm × 18 mm × 1.5 mm so that 45 mm × 18 mm single-sided surface roughness shown in Table 3 Polished.

  c. PPS resin composition 1: A rod-shaped molded article of 65 mm × 13 mm × 6.5 mm obtained by injection molding the PPS resin composition 1 at a cylinder temperature of 320 ° C., a mold temperature of 150 ° C., an injection speed of 20 mm / sec and a holding pressure of 60 MPa. The surface of 13 mm × 6.5 mm was polished to have the surface roughness shown in Table 3.

<Production of First Member (Formation of Particle Layer)>
The substrate is immersed in a liquid containing 15% by mass of silica fine particles having a particle size of 25 nm in isopropyl alcohol, and then pulled up once such that the polishing surface is perpendicular to the liquid surface. Silica fine particles were applied to the polished surface of the material by the advective flow accumulation method, dried at 23 ° C. to volatilize isopropyl alcohol, and an inorganic particle layer was formed on the surface of the substrate to produce a first member.

<Manufacture of composite member (joining with second member)>
a. About the aluminum base material, the composite member as shown to FIG. 1, 2 was manufactured by insert molding by inject-molding the 2nd member which consists of PPS resin composition 1 similarly to evaluation of the above-mentioned joint strength.

b. For the glass substrate, PPS resin composition 1 is injection molded in advance under the same molding conditions as the above-mentioned evaluation of bonding strength to obtain a rod-shaped molded article of 80 mm × 10 mm × 4 mm, and this 80 mm × 10 mm surface Heat plate welding is performed so that the area of the end 10 mm × 10 mm overlaps 10 mm from the 18 mm side edge of the inorganic particle layer forming surface of the glass substrate, and the same composite member as the aluminum base insert molded article Molded.
Here, as a condition of the hot plate welding, the bonding surface of the glass substrate and the rod-shaped molded product is heated on a hot plate at 320 ° C. respectively, and the bonding surface of the rod-shaped molded product is softened. After being brought into contact with the bonding surface and pressurized at 3 MPa, the rod-shaped molded product was solidified by standing at room temperature.

  c. As for the PPS resin composition 1 base material, for injection molding having a cavity of 130 mm × 13 mm × 6.5 mm so that the 13 mm × 6.5 mm surface on which the inorganic particle layer is formed is exposed to the space in the cavity. A mold is inserted, and the PPS resin composition 1 is injection molded under the same molding conditions as the above-mentioned evaluation of bonding strength, and the molten resin is injected onto the inorganic particle layer forming surface of the inserted first member 1 The second member 2 was provided by insert molding, and a 130 mm × 13 mm × 6.5 mm composite member shown in FIG. 6B was manufactured.

<Evaluation of joint strength>
For composite members using an aluminum base and a glass base, the bonding strength was measured using the jig shown in FIG. 3 and the PPS resin composition 1 base was used, as in the above-described evaluation of the bonding strength. About a composite member, the tension test was carried out by Orientec Co., Ltd. Tensilon UTA-50kN (cross head speed 10 mm / min), and the joint strength of the composite member was measured. The bonding strength evaluation results according to the following criteria are shown in Table 3.

:: bonding strength 30 MPa or more ○: bonding strength 20 MPa or more, less than 30 MPa Δ: bonding strength 10 MPa or more, less than 20 MPa

[Influence evaluation of inorganic particle layer]
An aluminum substrate, a glass substrate, and a PPS resin composition 1 substrate similar to the above-described evaluation of the effects of the substrate type and surface roughness are prepared so that Rmax = 4 μm and Rz = 4 μm, and isopropyl alcohol The first member was manufactured by immersing in a liquid in which silica particles having an average particle diameter of 25 nm are dispersed. Here, the thickness of the inorganic particle layer was changed as shown in Table 4 by adjusting the silica particle concentration in the liquid and the number of times of immersion of the substrate.

  The other members were manufactured in the same manner as in the above-described evaluation of the effects of the substrate type and the surface roughness, and a composite member bonded to the second member made of the PPS resin composition 1 was manufactured, and the bonding strength was evaluated. The results are shown in Table 4.

  In the example using a glass as the base material and a COC resin composition as the second member, a composite member in which the bonding portion between the first member and the second member is transparent is obtained, and the composite member of the present invention is transparent. It has been confirmed that it is applicable to member applications.

[Comparison with other dissimilar bonding technology]
Aluminum cut as 45 mm x 18 mm x 1.5 mm as a substrate: A plate of "A5052" manufactured by Nippon Light Metal Co., Ltd. was subjected to NMT treatment by Taisei Plus Co., Ltd. known as a kind of chemical etching to roughen the surface As a first member, it is joined to the second member composed of PPS resin composition 1 under the same molding conditions and test conditions as the above-mentioned evaluation of the joint strength, and the joint strength is measured. As a result, the joint strength is 30 MPa Met.

  Moreover, also about the 2nd member which consists of LCP resin composition 2, as a result of performing joint strength evaluation with the 1st member which performed the NMT process to the aluminum base similarly, joint strength was 15 Mpa. Furthermore, the bonding strength was compared with the sample (bonding strength 33 MPa) described in Example 4 of JP-A-2014-117724. From these results, it was confirmed that the composite member of the present invention can obtain the same or higher bonding strength as compared with the conventional bonding technology.

1 First member 2 Second member 3 Bonding strength test piece pressing jig 4 Bonding strength test piece fixing jig 5 Sample for evaluation of air tightness H Hole formed in the center of sample for air tightness evaluation 7 Airtightness testing machine
8 Airtightness tester body 9 Airtightness tester lid 10 O-ring 11 Distilled water 12 Line 13 Airtightness tester body P inside pressure

Claims (15)

  Consisting of a first member having a layer consisting of inorganic particles on a base material, and a resin composition in which the shrinkage factor sh (%) and elastic modulus E (MPa) satisfy E ≦ 100000 × exp (−2.64 × sh) And a second member.   The composite according to claim 1, wherein the second member is made of a resin composition in which a shrinkage ratio sh (%) and an elastic modulus E (MPa) satisfy E 6 63000 x exp (-2.64 x sh). Element.   The composite member according to claim 1, wherein the resin composition contains an elastomer.   The composite member formed by joining the 1st member which has a layer which consists of inorganic particles on a base material, and the 2nd member which consists of a resin composition containing an elastomer. The composite member according to claim 3 or 4, wherein the elastomer is at least one selected from an olefin polymer, a polyester elastomer, a urethane elastomer, and an acrylic polymer.   The composite member according to any one of claims 3 to 5, wherein the elastomer is an elastomer containing glycidyl group. The composite member according to any one of claims 1 to 6, wherein the layer composed of the inorganic particles is composed of inorganic particles having an average particle diameter of 1 to 500 nm. The composite member according to any one of claims 1 to 7, wherein the layer made of the inorganic particles has a thickness of 1 to 1,500 nm.   The composite member according to any one of claims 1 to 8, wherein the layer composed of the inorganic particles is composed of closely packed inorganic particles.   The composite according to any one of claims 1 to 9, wherein the base material has a surface roughness measured according to JIS B 0601: 1982, Rz = Rmax ± 10%, and Rmax = 1 to 10 μm. Element.   The composite member according to any one of claims 1 to 10, wherein the layer on the substrate substantially consists of only the inorganic particles.   The composite member according to any one of claims 1 to 11, wherein the resin composition contains 5 to 50% by mass of a filler composed of inorganic particles having a particle diameter of 0.1 to 50 m.   The composite member according to any one of claims 1 to 12, wherein the substrate is made of at least one selected from resin, glass, and ceramic.   The composite member according to any one of claims 1 to 13, wherein the thermal conductivity λ (W / m · k) of the base material is 2.0 or less. The method of manufacturing a composite member according to any one of claims 1 to 14, wherein the first member is formed by forming a layer composed of inorganic particles on a base material by an advection accumulation method. A composite member in which a second member made of a resin composition having a shrinkage ratio sh (%) and an elastic modulus E (MPa) satisfying E ≦ 100000 × exp (−2.64 × sh) is joined by injection molding. Production method.

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