JP4521657B2 - Adhesion method and adhesion pretreatment method - Google Patents

Description

  The present invention relates to an adhesion method and an adhesion pretreatment method, and more specifically, a method of adhering another member to the surface of a substrate made of a carbon atom-containing material such as a resin via an adhesive layer, and a pretreatment for the method. Regarding the method.

  Olefin resins with no polar group in the resin skeleton (polypropylene (PP), polyethylene (PE), etc.), polyphenylene sulfide (PPS) and polybutylene terephthalate (PBT) used for electrical parts, silicone resins, silicone rubbers, fluororesins In addition, resin materials such as fluororubber are not familiar with adhesives, and it has been difficult to bond such difficult-to-adhere resin materials to other members with high adhesive strength (adhesion reliability).

  Therefore, in the past, as a pretreatment method when bonding such a hardly adhesive resin material to other members, the surface is etched with a strong oxidizing agent (potassium dichromate, etc.) to increase the surface area and the surface. Active functional groups (hydroxyl group, carbonyl group, etc.) were formed to increase the adhesive strength. However, since many oxidizers used in such a method are generally concerned with toxicity, care must be taken in handling, and strong oxidizers cause cracks in the resin, resulting in cracks and reduced strength. There was a problem that there was a risk of causing.

Japanese Laid-Open Patent Publication No. 10-139901 (Patent Document 1) discloses a method of joining other materials via an adhesive after activating the surface of a vulcanized rubber by irradiating ultraviolet rays. . However, in the method disclosed in Patent Document 1, since the spot area irradiated with ultraviolet rays is at most 1 cm ² , it is difficult to treat a large area uniformly, and the activated surface is relatively early. Therefore, there is a problem in that there is a great restriction on the process because the process must be shifted to the bonding process immediately after the pretreatment.
JP-A-10-139901

  The present invention has been made in view of the above-described problems of the prior art, and has high adhesion on a base material (hereinafter referred to as “carbon atom-containing base material”) made of a carbon atom-containing material such as a so-called hardly adhesive resin. It is possible to form an adhesive layer with strength, and a high level of adhesion reliability and fatigue resistance can be achieved by adhering to other members via the adhesive layer, and the activated resin surface It is an object of the present invention to provide an adhesion method capable of maintaining the active state of the above for a long time, causing no processing unevenness, and avoiding the adverse effects of using a strong oxidizing agent, and an adhesion pretreatment method therefor.

  As a result of intensive studies to achieve the above object, the present inventors, as a pretreatment for adhesion, irradiate the surface of the carbon atom-containing substrate with vacuum ultraviolet light having a wavelength of 50 nm to 100 nm and / or metal atoms and / or It has been found that the above object can be achieved by attaching scattered particles containing carbon atoms, and the present invention has been completed.

That is, the bonding method of the present invention is:
In a reduced pressure state of 1 Torr or less, or in the atmosphere of at least one kind of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas , the surface of the resin base material as a base material made of a carbon atom-containing material An adhesion pretreatment step of attaching scattered particles containing metal atoms and / or carbon atoms while irradiating vacuum ultraviolet light having a wavelength of 50 nm to 100 nm;
An adhesive step of forming an adhesive layer by applying an adhesive on the surface of the base material to which the scattered particles are adhered, and bonding the base material and another member via the adhesive layer;
It is the adhesion | attachment method characterized by including.

In addition, the pre-bonding treatment method of the present invention is a method comprising a carbon atom-containing material in a reduced pressure state of 1 Torr or less or at least one shield gas atmosphere selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas. It is an adhesion pretreatment method characterized in that scattered particles containing metal atoms and / or carbon atoms are attached to a surface of a resin base material as a base material while irradiating vacuum ultraviolet light with a wavelength of 50 nm to 100 nm.

In the bonding method and the bonding pretreatment method of the present invention, the vacuum ultraviolet light and the scattered particles have a pulse width of 100 on a target made of at least one material selected from the group consisting of metal, metal compound and carbon. It is preferably generated by irradiation with a pulse laser beam having a picosecond to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ² .

Although the reason why the adhesive layer is formed with sufficient adhesive strength on the carbon atom-containing substrate by the above-described method of the present invention is not necessarily clear, the present inventors infer as follows. That is, a target made of at least one material selected from the group consisting of metals, metal compounds and carbon has a pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W / cm ² to 10 ¹² W / cm ^2. When the pulse laser beam is irradiated, high-temperature plasma is formed on the target surface, and vacuum ultraviolet light having a wavelength of 50 nm to 100 nm is generated from the plasma. Since such vacuum ultraviolet light has a high absorption rate with respect to the carbon atom-containing material, when this vacuum ultraviolet light is irradiated onto the carbon atom-containing substrate, p electrons, which are outer electrons of carbon atoms, are excited on the surface of the substrate. Alternatively, ionization breaks the bond between the carbon atom and the atom bonded to the carbon atom, and the surface of the carbon atom-containing substrate is activated to form an active end. On the other hand, atoms or molecules containing metal atoms and / or carbon atoms are scattered with high energy from the target surface irradiated with the laser light depending on the material constituting the target, and are heated inside or by the plasma. At the target surface, neutral atoms and ions formed by evaporation of the material constituting the target, and clusters formed by combining some of the molecules, neutral atoms and ions, have high energy. Scatter. And, when such scattered particles reach the carbon atom-containing base material activated by the vacuum ultraviolet light, the scattered particles have high energy and thus adhere firmly to the base material, and the active ends are scattered by the scattered particles. The substrate surface is fixed and maintained in an active state. Therefore, according to the method of the present invention, the base material surface is maintained in an active state without unevenness over a long period of time, and when the adhesive is applied on the base material surface thus activated, the adhesive The present inventors speculate that the adhesive layer is formed with high adhesive strength by firmly bonding to the active terminal.

Here, the vacuum ultraviolet light having a wavelength of 50 nm to 100 nm means vacuum ultraviolet light having at least a part of wavelengths in the wavelength region of 50 nm to 100 nm, and satisfying at least one of the following conditions: Preferably it is.
(i) having at least one peak of light intensity in a wavelength region of 50 nm to 100 nm;
(ii) the total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 100 nm to 150 nm;
(iii) The total energy of light in the wavelength region of 50 nm to 100 nm is higher than the total energy of light in the wavelength region of 50 nm or less.
(iv) The energy density of light in the wavelength region of 50 nm to 100 nm is 0.1 μJ / cm ^{2 to} 10 mJ / cm ² (more preferably 1 μJ / cm ^{2 to} 100 μJ / cm ² ) on the substrate. In addition, when the energy density on the substrate is lower than 0.1 μJ / cm ² , the time required for the treatment tends to be excessively long. On the other hand, when the energy density is higher than 10 mJ / cm ^{2, the} substrate is decomposed. There is a tendency.

Furthermore, in the bonding method and bonding pretreatment method of the present invention, it is preferable that the scattered particles adhere to the surface of the olefin-based resin substrate in a vacuum state of 1 × 10 ⁻³ Torr or less in the container. When using a container whose inside is in a reduced pressure state in this way, the vacuum ultraviolet light is irradiated to the surface of the carbon atom-containing substrate without being absorbed by the vacuum ultraviolet light absorbing material such as oxygen in the air, and the carbon atom containing The substrate surface tends to be activated more efficiently. In addition, when the treatment is performed in a shield gas atmosphere, the vacuum ultraviolet light is irradiated to the surface of the carbon atom-containing substrate without being absorbed by the vacuum ultraviolet light absorbing material without being in a reduced pressure state, and the carbon atom-containing substrate surface is more efficient. It tends to be well activated. Further, in the latter case, it is not necessary to use a vacuum pump or a pressure vessel as compared with the former case, and therefore, it tends to be more preferable in terms of simplicity of the apparatus and low cost.

  According to the adhesion pretreatment method of the present invention, the surface of a carbon atom-containing substrate that has been uniformly activated by vacuum ultraviolet light is maintained in an active state for a long time by the adhesion of scattered particles. According to the bonding method of the present invention, since the adhesive is applied onto the surface of the substrate thus activated, the adhesive and the substrate surface are firmly bonded, and the high bonding strength It becomes possible to form an adhesive layer. Therefore, according to the present invention, even if it is a carbon atom-containing substrate such as a so-called difficult-to-adhere resin, a high level of adhesion reliability and fatigue resistance can be achieved when bonded to other members, and a strong oxidizing agent It is no longer necessary to use, and the occurrence of processing unevenness is sufficiently suppressed, and further, the pre-bonding treatment step and the bonding step can be performed separately and independently.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. First, the adhesion pretreatment method of the present invention will be described.

FIG. 1 is a schematic diagram showing a basic configuration of an embodiment of an adhesion pretreatment apparatus suitable for carrying out the adhesion pretreatment method of the present invention. The adhesion pretreatment apparatus shown in FIG. 1 is a so-called laser ablation apparatus 1. It is configured as. That is, the laser ablation apparatus 1 shown in FIG. 1 includes a laser light source 2 and a processing container 3 into which the laser light L ₁ emitted from the laser light source 2 is introduced. A target 4 irradiated with L ₁ and a base material 6 on which an activated surface layer 5 is to be formed are disposed.

The laser light source 2 is not particularly limited as long as it is a laser light generator capable of emitting a pulse laser beam having a pulse width of 100 picoseconds to 100 nanoseconds. For example, the laser light source 2 includes a YAG laser device or an excimer laser device. In particular, it is preferable to be constituted by a YAG laser device. Then, the laser light source 2 is disposed at a position irradiated with laser light L ₁ towards the target 4 which is located inside the treatment container 3. Further, although not shown, a metal atom and / or scattering particles a and vacuum ultraviolet light L ₂ containing a carbon atom efficiently generated from the surface of the target 4 when irradiated with laser light L ₁ to the target 4 as it may adjust the energy density and irradiation angle of the laser beam middle lens of the optical path of the laser light L _1, a mirror or the like appropriately arranged. In particular, a condenser lens (not shown) is disposed inside or outside the processing container 3 so that the irradiation intensity of the pulsed laser light L ₁ applied to the target 4 is 10 ⁶ W / cm ² to 10 ¹² W / cm. ² is preferable, and 10 ⁸ W / cm ² to 10 ¹¹ W / cm ² is particularly preferable.

The processing container 3 is a container (for example, a stainless steel container) for accommodating at least the target 4 and the base material 6 therein, and introduces the laser beam L ₁ into the surface of the target 4 disposed in the container 3. A window 7 (for example, a quartz window) is provided. Further, a vacuum pump (not shown) is connected to the processing container 3 so that the inside of the container 3 can be maintained in a reduced pressure state of a predetermined pressure. When the container 3 whose inside is in a reduced pressure state is used in this way, the vacuum ultraviolet light L ₂ is irradiated on the surface of the base material 6 without being absorbed by a vacuum ultraviolet light absorbing material such as oxygen in the air. Is activated more efficiently. In addition, as a pressure at the time of maintaining the inside of the container 3 in a pressure-reduced state, it is a pressure of 1 Torr or less, and a vacuum state of 1 × 10 ⁻³ Torr or less is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 1 Torr or less.

The target 4 only needs to be made of a material that generates scattered particles containing metal atoms and / or carbon atoms by irradiation with the laser beam L ₁ described above, and is at least selected from the group consisting of metals, metal compounds, and carbon. One made of one material is preferable. As such a metal material, various transition element metals, typical element metals, metalloids, or alloys thereof can be used, for example, Cu, Al, Ti, Si, Cr, Pt, Au, Ag, Pd, Zr, Mg, Ni, Fe, Co, Zn, Sn, W, Be, Ge, Mn, Mo, Nb, Ta, Hf, alloys containing them as main components, etc., among others, Cu, Al Ti, Si, Zn, Fe, and Ni are preferable because they are inexpensive and have low toxicity. The metal material here may be, for example, a semiconductor such as silicon, germanium, silicon carbide, gallium arsenide, InP, or ZnTe. Examples of the metal compound material include various transition element metals, oxides, nitrides, carbides, etc. of typical element metals or metalloids. Among them, Al ₂ O ₃ , AlN, Si ₃ N ₄ , SiO ₂ , SiO ₂ , TiO ₂ , TiN, and ZnO ₂ are preferable. In addition, the metal compound material here may contain a plurality of metal elements, and may further contain a non-metal element. Examples of the carbon material include various amorphous carbons, graphite, and the like, and those having high purity are preferable. Furthermore, the target 4 may be a composite material of such a metal material, a metal compound material, and a carbon material. The shape of the target 4 is not particularly limited, and a bulk material made of the target material formed into a plate shape, a rod shape, or the like, a tape target formed by applying the target material on a tape, vapor deposition, or the like Can be used.

The base material 6 is a base material made of a carbon atom-containing material to which other members are to be bonded via an adhesive layer in the bonding step described later on the surface. It is determined. Such a base material made of carbon-containing material, Ru can be used tree Aburamoto material. Such resin base materials include olefin resins {polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, ethylene. -Propylene-diene copolymer, ethylene-butene-diene copolymer, polymethylpentene, etc.}, butyl rubber, polyester, polycarbonate, polyacetal, polyamide, polyamideimide, polyetherimide, polyphenylene ether, polyphenylene sulfide, polyether Sulphone, polyether ketone, polyphthalamide, polyether nitrile, polybenzimidazole, polycarbodiimide, acrylic resin {polymethyl (meth) acrylate, poly ( ) Acrylamide, etc.}, acrylic rubber, fluororesin {poly-4-fluorinated ethylene, etc.}, fluororubber, liquid crystal polymer, epoxy resin, melamine resin, urea resin, diallyl phthalate resin, phenol resin, polysilane, silicone resin (polysiloxane, etc.) ), Silicone rubber, urethane resin, styrene resin {polystyrene, styrene-butadiene copolymer, styrene-hydrogenated butadiene copolymer, etc.}, polymers such as polyethylene terephthalate, polybutylene terephthalate, polyvinyl chloride, polyvinylidene chloride ( Homopolymers or copolymers), and base materials composed of laminates thereof.

  Further, according to the present invention, an adhesive layer can be formed with a high degree of adhesive strength. Therefore, the present invention is a so-called hardly adhesive resin such as an olefin resin (TSOP manufactured by Nippon Polychem Co., Ltd., trade name: PC-6). ), Polypropylene, polyethylene, polyphenylene sulfide, polybutylene terephthalate, silicone resin, silicone rubber, fluororesin, fluororubber and the like.

  The shape and thickness of the base material 6 made of such a carbon atom-containing material are not particularly limited, and a film, plate, various shapes of molded products, and the like are appropriately selected depending on the use of the product to be obtained. Further, the thickness of the activated surface layer 5 to be formed on the surface of the substrate 6 is not particularly limited, and the adhesive strength between the adhesive layer formed in the bonding step described later and the substrate is optimal. However, it is generally preferably about 1 nm to 1 mm, more preferably about 10 nm to 0.01 mm, and particularly preferably about 20 nm to 0.001 mm.

The positional relationship between the base material 6 and the target 4 is not particularly limited, and the surface of the base material 6 is reliably irradiated with the vacuum ultraviolet light L ₂ generated from the surface of the target 4 and the scattered particles a are efficiently attached. Thus, the base material 6 is appropriately disposed with respect to the target 4, and in FIG. 1, the base material 6 is disposed at a position where the angle Θ with respect to the normal line of the target 4 is 45 °. In addition, a target driving device (for example, a target turntable, not shown) is connected to the target 4, and a fresh surface of the target (laser light non-irradiated surface) is sequentially fed out to the irradiation position of the laser light L _1. ing. Further, a substrate driving device (for example, a substrate turntable, not shown) may be connected to the substrate 6 so that the surface of the substrate 6 is activated more uniformly.

As mentioned above, although one Embodiment of the adhesion pretreatment apparatus suitable for implementing the adhesion pretreatment method of this invention was described, the apparatus suitable for this invention is not limited to the said embodiment. That is, for example, in the above embodiment, the processing container 3 is connected to a vacuum pump (not shown), but at least one kind of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas is introduced. In this case, the interior of the container 3 can be maintained in a predetermined shielding gas atmosphere. With such internal use container 3 which is a shielding gas atmosphere, the surface of the substrate 6 without without a container 3 and a vacuum is vacuum ultraviolet light L ₂ is absorbed in the vacuum ultraviolet light absorbing material Irradiated, the surface of the substrate 6 is activated more efficiently. Further, it is preferable to connect both a vacuum pump (not shown) and a gas cylinder (not shown) to the processing container 3 so that the inside of the container 3 has a predetermined shielding gas atmosphere and is maintained at a predetermined pressure condition. is there. As such conditions, for example, a pressure of atmospheric pressure or lower in a helium gas atmosphere is preferable, and a pressure of 500 Torr or lower is more preferable. In addition, it is preferable that the oxygen partial pressure and / or the nitrogen partial pressure be 1 Torr or less.

In the above embodiment, the laser light source 2 is disposed outside the processing container 3. However, the laser light source 2 may be disposed inside the processing container 3, in which case the laser light L ₁ is introduced into the container 3. This window 7 becomes unnecessary.

Furthermore, in the said embodiment, although the base material 6 is arrange | positioned in the position where the angle (theta) with respect to the normal line of the target 4 is 45 degrees, it is not specifically limited to such a positional relationship, The normal line of the target 4 The substrate 6 may be disposed at a position where the angle Θ relative to the angle is in the range of about 10 ° to 60 °. Further, for example, a base material 6 made of a carbon atom-containing material that can transmit the laser light L ₁ is used, and the base material 6 is disposed between the laser light source 2 and the target 4 so as to face the target 4. The target 4 may be irradiated with the laser light L _{1 that} has passed through the target 6.

In addition, a target 4 that can transmit the laser light L ₁ is used, the target 4 is disposed between the laser light source 2 and the substrate 6, and the surface (target material side) from the back surface (transparent film side) of the target 4. Alternatively, the vacuum ultraviolet light L ₂ and scattered particles a may be generated from the surface (target material side) of the target 4 by the laser light L ₁ transmitted through the laser beam L ₁ and supplied to the surface of the substrate 6. With such a configuration, pre-bonding treatment for a relatively large base material tends to be easier. Moreover, as a target used for such a structure, the tape-shaped target which laminated | stacked the above-mentioned target material on the film (for example, PET, PE film) transparent with respect to a laser beam by vapor deposition, sticking, etc. is preferable.

  Next, a preferred embodiment of the adhesion pretreatment method of the present invention will be described with reference to FIG.

In the adhesion pretreatment method of the present invention, the pulsed laser light L ₁ having a pulse width 100 picoseconds to 100 nanoseconds it is irradiated from the laser light source 2 to the target 4 described above. Then, a high-temperature plasma P is formed on the surface of the target 4, and vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is generated from the plasma P. At the same time, from the surface of the target 4 irradiated with the laser beam L _1, molecules containing metal atoms or carbon atoms scatter with high energy depending on the material constituting the target. From the surface of the heated target 4, neutral atoms and ions formed by decomposition of the molecules constituting the target and some of the molecules, neutral atoms and ions are combined to form. Clusters are scattered with high energy. The pulse width of the pulsed laser light L ₁ becomes such that light having a wavelength less than 50nm because the laser energy in a short time is less than 100 picoseconds is irradiated to the target to concentrate produced, while the 100 nanosecond If exceeded, the energy of the laser is not sufficiently concentrated in time, and the wavelength of the generated light exceeds 100 nm. Further, in both cases where the wavelength of the generated light L ₂ is less than 50 nm and more than 100 nm, the absorption rate of the light L ₂ with respect to the carbon atom-containing material is lowered, and the surface of the carbon atom-containing substrate is sufficiently activated. In other words, the adhesive strength between the adhesive layer formed in the bonding step described later and the substrate is insufficient. Further, it is preferred that the irradiation intensity of the pulsed laser light _{L 1} irradiated to the target 4 is ^{10 6 W / cm 2 ~10 12} W / cm 2. When the irradiation intensity of the pulse laser beam L ₁ is less than 10 ⁶ W / cm ^2, there is a tendency that the vacuum ultraviolet light L ₂ having a wavelength of 50 nm to 100 nm is not sufficiently generated, and when exceeding 10 ¹² W / cm ² , the target is irradiated. are for main wavelength region of electromagnetic wave generated is in a wavelength range 50nm when the tends to amount of vacuum ultraviolet light L ₂ having a wavelength 50nm~100nm decreases.

The various scattering particles (ablator) a generated from the surface of the target 4 by irradiation of such a pulse laser beam L ₁ is supplied to the surface of the carbon-containing substrate 6 with a vacuum ultraviolet light L _2. Since the vacuum ultraviolet light L ₂ irradiated to the surface of the substrate 6 in the high absorption rate for carbon-containing material, the surface of the vacuum ultraviolet light L ₂ carbon atoms containing substrate 6 which is irradiated is sufficiently Activated. Since the scattered particles a reach there with high energy, the scattered particles a firmly adhere to the substrate 6 and the surface of the substrate is maintained in an active state. In this way, the surface of the carbon atom-containing substrate 6 is maintained in an active state without unevenness over a long period of time, and an adhesive is applied to the surface of the substrate thus activated in the bonding step described later. When applied, the adhesive and the substrate surface are firmly bonded to form an adhesive layer with high adhesive strength.

  In the above-described pre-bonding treatment method of the present invention, it is not necessary to heat the substrate to a high temperature when activating the surface of the substrate 6, and the substrate temperature is not particularly limited. What is necessary is just about ~ 50 degreeC. Further, the time required for activating the surface of the substrate 6 (laser light irradiation time) is not particularly limited, so that the adhesive strength between the adhesive layer formed in the bonding step described later and the substrate is optimized. Generally, it is preferably about 0.1 second to 10 minutes, and particularly preferably about 1 second to 1 minute.

  Next, the bonding method of the present invention will be described. In the bonding method of the present invention, an adhesive layer is formed by applying an adhesive on the surface of the substrate that is maintained in an active state by the vacuum ultraviolet light and scattered particles in the above-described bonding pretreatment process. And an adhering step of adhering the base material and the other member through the adhesive layer.

  The adhesive used here is not particularly limited, and is appropriately selected depending on the use of the product to be obtained, the base material to be used, and the like. Examples of such adhesives include thermosetting resin adhesives mainly composed of phenol resin, resorcin resin, furan resin, urea resin, melamine resin, polyester resin, polyurethane resin, epoxy resin, and silicone resin; polyvinyl acetate , Thermoplastic resin adhesives mainly composed of polyvinyl alcohol, polyvinyl chloride, polyvinyl butyral, polyacrylic acid ester, nitrocellulose, etc .; elastomer adhesives mainly composed of butadiene acrylonitrile rubber, neoprene, etc. Epoxy adhesives, acrylic adhesives, and cyanoacrylate adhesives are preferred.

  In addition, the thickness of the adhesive layer formed on the surface of the substrate is not particularly limited, and is appropriately determined depending on the use of the product to be obtained, the adhesive used, and the like, but generally about 10 nm to 1 mm is preferable. About 100 nm to about 0.5 mm is more preferable, and about 200 nm to about 0.1 mm is particularly preferable. Furthermore, the specific method of forming an adhesive layer by applying an adhesive on the surface of the substrate is not particularly limited, and examples of the application method include spraying, brush coating, and a method using a coating machine, At that time, the adhesive may be used as it is or diluted with a solvent or the like. Further, the method and conditions for solidifying the adhesive are not particularly limited, and are appropriately determined according to the adhesive to be used.

  In addition, other members that are bonded to such a carbon atom-containing substrate through the adhesive layer are not particularly limited, and metal members, resin members, woven fabrics, nonwoven fabric members, etc. The shape is appropriately selected, and the shape is appropriately selected according to the use of a product from which a molded body having a film shape, a plate shape, or various shapes can be obtained. In addition, when using the member which consists of resin like the above-mentioned hardly-adhesive resin as another member, it is preferable to also activate the adhesion surface of another member previously by the adhesion | attachment pre-processing method of this invention.

  In the bonding method of the present invention, an adhesive is applied to the surface of the substrate that is maintained in an active state by vacuum ultraviolet light and scattered particles in the above-described pre-bonding treatment step, and another member is applied to the adhesive layer. In order to solidify the adhesive on top of each other, the adhesive and the substrate surface are firmly bonded, and furthermore, a high level of adhesion reliability and resistance between the substrate and other members via the adhesive layer. Fatigue is achieved. In addition, since the substrate surface activated in the above-described pre-bonding process is maintained in an active state for a long time, it is not always necessary to perform the bonding process immediately after the above-mentioned pre-bonding process. Even if the bonding process is performed after about one month or more has elapsed since the execution of the treatment process, a high degree of adhesive strength is achieved.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

(Examples 1-3)
[Adhesion pretreatment process]
The laser light source 2 is a YAG laser device (Spectra Physics, trade name: PRO-290), the processing vessel 3 is a vacuum vessel with a quartz window (made of stainless steel, capacity 20 liters), and the target 4 is a carbon plate (diameter 30 mm, The adhesion pretreatment apparatus shown in FIG. 1 was produced using an olefin resin substrate (TSOP manufactured by Nippon Polychem Co., Ltd., trade name: PC-6, 30 mm × 30 mm × 3 mm) as the substrate 6. In addition, the base material 6 was arrange | positioned in the position where angle (theta) with respect to the normal line of the target 4 becomes 45 degrees, and the distance (distance between centers) between the base material 6 and the target 4 was 120 mm.

Next, using the manufactured apparatus, the inside of the container 3 is brought into a vacuum state in which the pressure is 10 ⁻³ Torr or less, the target 4 is rotated at 12 rpm, and the substrate 6 is rotated at 100 rpm, and the wavelength from the laser light source 2 is 532 nm. , Irradiation intensity shown in Table 1 {1.3 × 10 ⁹ W / cm ² (1.3 GW / cm ² ) to 1.81 × 10 ¹⁰ W / cm ² (18.1 GW / cm ² )}, pulse width 7 the pulsed laser light L ₁ nanosecond was irradiated to the target 4. Container 3 pulsed laser light L ₁ for internal vacuum state reaches the target 4 without attenuation, the surface of the target 4 hot plasma P is formed, the vacuum ultraviolet light having a wavelength in the range of 50nm~100nm L ₂ is generated, and at the same time, scattered particles (ablators) a such as clusters formed by combining neutral atoms and ions of carbon and some of these neutral atoms and ions from the surface of the target 4 are formed. Scattered. Then, the surface of the resin substrate 6 was irradiated with the vacuum ultraviolet light L ₂ generated from the plasma P and sufficiently activated, and the scattered particles a reached and adhered with high energy. The irradiation time was 30 seconds and the substrate temperature was about 25 ° C.

[Adhesion process]
Applying an adhesive (manufactured by Nichiban Co., Ltd., Araldite Standard 24 hour curing type) on the surface of the resin substrate 6 whose surface has been activated in the adhesion pretreatment step so that the thickness of the adhesive layer is about 50 μm, Furthermore, the adhesive is in contact with the upper surface of a test jig (a cylindrical member made of S45C having a diameter of 16 mm and a height of 38 mm) used for the film adhesion strength test apparatus described in JP-A-10-111234. Was cured. The curing conditions were 12 hours at 40 ° C. The test jig corresponds to the adhesive member 2 described in JP-A-10-111234, and is provided with a through-hole orthogonal to the axial direction of the cylinder as described in the publication.

[Tensile test]
First, an adhesive (manufactured by Nichiban Co., Ltd., Araldite Standard 24-hour curing type) is used on the back surface of the resin substrate 6 bonded to the test jig via the adhesive (the surface opposite to the surface bonded to the test jig). Then, a cold-rolled steel plate (30 mm × 30 mm × 0.7 mm) previously polished with water-resistant abrasive paper # 1000 was adhered to reinforce the resin substrate 6.

  Next, the resin base material 6 bonded to the test jig is attached to a tensile tester (manufactured by Shimadzu Corp., Autograph DSS5000) using a film adhesion strength test instrument described in JP-A-10-111234, and tested. The jig was pulled at a pulling speed of 5 mm / min in the direction in which the jig was peeled off from the resin substrate 6.

  As a result, the load (maximum load) at the moment when the test jig was peeled off from the resin base material 6 was measured as the adhesive strength, and the obtained results are shown in Table 1. Also, whether the peeled state is a peeled form at the interface between the resin substrate and the adhesive layer (“interface”) or a peeled form in which the adhesive layer is partially cohesive (“partial cohesive failure”) The adhesive layer was observed as a whole in a cohesive failure peeled form (“cohesive failure”), and the results obtained are also shown in Table 1.

(Examples 4 to 8)
A polypropylene plate (Novatec MA2 manufactured by Nippon Polychem Co., Ltd. was molded into a flat plate of 150 mm × 150 mm × 3 mm and cut into 30 mm × 30 mm × 3 mm) as the substrate 6 and the irradiation intensity of the pulse laser beam is shown in Table 1. The adhesion pretreatment process and the adhesion process were carried out in the same manner as in Example 1 except that the values shown in Table 1 were used, and the tensile test was carried out in the same manner as in Example 1. The obtained results are shown in Table 1.

(Examples 9 to 13)
A polyethylene plate (Novatec HDHJ490 manufactured by Nippon Polychem Co., Ltd. was molded into a 150 mm × 150 mm × 3 mm flat plate and cut into 30 mm × 30 mm × 3 mm) was used as the base material 6 and the irradiation intensity of pulsed laser light was shown in Table 1. The adhesion pretreatment process and the adhesion process were carried out in the same manner as in Example 1 except that the values shown in Table 1 were used, and the tensile test was carried out in the same manner as in Example 1. The obtained results are shown in Table 1.

(Comparative Examples 1-3)
Tensile tests were performed in the same manner as in Examples 1, 4 and 9, except that the bonding step was performed without performing the bonding pretreatment step, and the adhesive layer was directly formed on the surface of the resin substrate. . The obtained results are shown in Table 1.

（実施例１４〜１５）
ターゲット４として銅板（直径３０ｍｍ、厚さ４ｍｍ）を用い、パルスレーザー光の照射強度を１．５×１０^９Ｗ／ｃｍ^２（１．５ＧＷ／ｃｍ^２：実施例１４）又は３．３×１０^９Ｗ／ｃｍ^２（３．３ＧＷ／ｃｍ^２：実施例１５）とした以外は実施例１と同様にして接着前処理工程及び接着工程を実施し、実施例１と同様にして引張試験を行った。

(Examples 14 to 15)
A copper plate (diameter 30 mm, thickness 4 mm) was used as the target 4, and the irradiation intensity of the pulse laser beam was 1.5 × 10 ⁹ W / cm ² (1.5 GW / cm ² : Example 14) or 3.3 × 10. Except for ⁹ W / cm ² (3.3 GW / cm ² : Example 15), the pre-bonding treatment step and the bonding step were performed in the same manner as in Example 1, and the tensile test was performed in the same manner as in Example 1. It was.

  As a result, when the resin base material obtained in Example 14 was used, the peeled state was a peeled form (partially cohesive failure) in which the adhesive layer was partially cohesive and obtained in Example 15. When the resin substrate was used, the peeled state was a peeled form (cohesive failure) in which the adhesive layer was totally cohesive.

(Comparative Example 4)
Using a silicon wafer (P-type silicon wafer, 100 surface, thickness 700 μm, manufactured by Komatsu Electronics Co., Ltd.) 8, the target 4, the silicon wafer 8, and the substrate 6 are placed in the positional relationship shown in FIG. Except that it was placed inside and the irradiation time of the pulse laser beam was 50 seconds, the same as in Example 2 (the target 4 was a carbon plate, the base material 6 was a TSOP base material, and the irradiation intensity was 4.5 GW / cm ² ). The adhesion pretreatment process and the adhesion process were performed, and a tensile test was performed in the same manner as in Example 2. When the silicon wafer 8 is arranged between the target 4 and the base material 6 in this way, the silicon wafer 8 reflects the vacuum ultraviolet light L ₂ by about 60%, so that the vacuum ultraviolet light L ₂ is reflected on the surface of the base material 6. However, the scattered particles (ablator) a were scattered only in front of the target 4, and thus did not reach the surface of the substrate 6.

  As a result, the adhesive strength was as low as 0.7 MPa, and the peeled state was a peeling form (interface peeling) at the interface between the resin substrate and the adhesive layer.

  As described above, according to the adhesion pretreatment method of the present invention, the surface of the carbon atom-containing substrate that has been uniformly activated by vacuum ultraviolet light is maintained in an active state for a long time by adhesion of scattered particles. It becomes like this. According to the bonding method of the present invention, the adhesive is applied on the surface of the substrate thus activated, and another member is stacked on the adhesive layer to solidify the adhesive. The adhesive and the substrate surface are firmly bonded, and a high level of adhesion reliability and fatigue resistance is achieved between the substrate and other members via the adhesive layer. Therefore, according to the present invention, adverse effects caused by using a strong oxidant can be avoided, the occurrence of processing unevenness can be sufficiently suppressed, and the pre-bonding treatment step and the bonding step can be performed independently. Become. Therefore, the present invention is very useful as an adhesion method capable of achieving high adhesion strength to a resin material such as a hardly-adhesive resin, and an adhesion pretreatment method therefor.

It is a schematic diagram which shows the basic composition of suitable one Embodiment of the adhesion | attachment pre-processing apparatus suitable for this invention. It is a schematic diagram which shows the positional relationship of the target in the comparative example 4, a silicon wafer, and a base material.

Explanation of symbols

1 ... bonding pretreatment device, 2 ... laser light source, 3 ... processing vessel 4 ... target, 5 ... activated surface layer, 6 ... carbon-containing substrate, 7 ... window, 8 ... silicon wafer, L ₁ ... Pulse laser light, L ₂ ... vacuum ultraviolet light, a ... scattered particles, P ... plasma.

Claims (6)

In a reduced pressure state of 1 Torr or less, or in the atmosphere of at least one kind of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas , the surface of the resin base material as a base material made of a carbon atom-containing material An adhesion pretreatment step of attaching scattered particles containing metal atoms and / or carbon atoms while irradiating vacuum ultraviolet light having a wavelength of 50 nm to 100 nm;
An adhesive step of forming an adhesive layer by applying an adhesive on the surface of the base material to which the scattered particles are adhered, and bonding the base material and another member via the adhesive layer;
A bonding method comprising the steps of: A pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W are applied to a target in which the vacuum ultraviolet light and the scattered particles are made of at least one material selected from the group consisting of metals, metal compounds, and carbon. The bonding method according to claim 1, wherein the bonding method is performed by irradiation with a pulsed laser beam of / cm ² to 10 ¹² W / cm ² . The adhesion method according to claim 1 or 2, wherein the scattering particles are adhered to the surface of the olefin-based resin base material in a vacuum state of 1 x ^10-3 Torr or less . In a reduced pressure state of 1 Torr or less, or in the atmosphere of at least one kind of shielding gas selected from the group consisting of hydrogen gas, helium gas, neon gas, and argon gas , the surface of the resin base material as a base material made of a carbon atom-containing material A pretreatment method for adhesion, comprising adhering scattered particles containing metal atoms and / or carbon atoms while irradiating vacuum ultraviolet light having a wavelength of 50 nm to 100 nm. A pulse width of 100 picoseconds to 100 nanoseconds and an irradiation intensity of 10 ⁶ W are applied to a target in which the vacuum ultraviolet light and the scattered particles are made of at least one material selected from the group consisting of metals, metal compounds, and carbon. The adhesion pretreatment method according to claim 4, wherein the adhesion pretreatment method is performed by irradiating a pulsed laser beam of / cm ² to 10 ¹² W / cm ² . The adhesion pretreatment method according to claim 4 or 5, wherein the scattered particles are adhered to the surface of the olefin-based resin substrate in a vacuum state of 1 x ^10-3 Torr or less .

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