JP3585253B2 - Adhesion method of resin tube - Google Patents

Abstract

PURPOSE:To simultaneously perform modification and bonding regardless of the region and diameter of a resin tube by interposing an adhesive and/or a compd. having functional group showing compatibility with respect to the tube between the resin tube and an article to be bonded and irradiating the tube with laser or ultraviolet rays of specific energy to bond the tube and the article to be bonded. CONSTITUTION:An adhesive and/or a compd. having a functional group showing compatibility with respect to the tube is interposed between the inner or outer wall of a resin tube and an article to be bonded and the tube is irradiated with laser or energy beam containing ultraviolet rays with photon energy of 80kcal/md or more from the exterior or interior or both of the interior or exterior thereof to chemically bond the tube and the adhesive and/or the compd. having the functional group showing compatibility with respect to the adhesive to bond the tube and the article to be bonded. That is, laser beam passes through a light path 7 and a mirror 2 from an excimer device 1 to be guided to a sample 3 and reaches the adhesive while it is absorbed into the resin tube 4 and the adhesive is cured to bond the tube 4 and the article 5 to be bonded.

Description

【００６１】
【発明の効果】
以上説明してきたように本発明は、チューブの径、部位に関わらず、改質と接着を同時に行う事が可能であり、また、改質後接着を行う際にも接着剤が限定されないため、短時間で、簡便に接着強さが向上し、人体に悪影響を及ぼす物質を使用しない安全な樹脂製チューブの接着方法となっている。
【図面の簡単な説明】
【図１】本発明の方法を実施するための装置の斜視図。
【図２】図１の装置の一部を拡大して示す断面図。
【図３】本発明の方法を実施するための他の装置の斜視図。
【図４】図３の装置の一部を拡大して示す説明図。
【図５】本発明の方法を実施するための他の装置の斜視図。
【図６】図５の装置の一部を拡大して示す断面図。
【図７】図６の装置の一部を模式的に示す説明図。
【図８】本発明の方法を実施するための他の装置の斜視図。
【図９】図８の装置の一部を拡大して示す断面図。
【図１０】図８の装置の一部を拡大して示す断面図。
【図１１】Ｘ線光電子分析法で分析を行い、試料にＸ線を入射して、そこから跳ね返ってくる光電子を検出器でカウントし、そのカウント量から試料がどの結合エネルギーを持っているかを示す図であり、本図はこの場合のレーザ照射前のエネルギー分布を示す線図。
【図１２】図１１に対応する図で、特にレーザ照射後のエネルギー分布を示す線図。
【符号の説明】
１…ＡｒＦエキシマレーザ、４…樹脂製チューブ、５…被接着物、６…接着剤、１４…導波路、１９…サンプル、２２…導波路、２３…サンプル、２７…加熱装置。[0001]
[Industrial applications]
The present invention relates to a method for bonding a resin having a tube shape.
[0002]
[Prior art]
Conventionally, in the bonding of resins, particularly in the case of difficult-to-bond materials such as fluororesin or PE, due to poor adhesion, chemical treatment such as sodium treatment or dichromic acid treatment, corona discharge treatment, or ultraviolet light Pretreatment such as laser treatment is indispensable, and the adhesion has been performed using an adhesive after increasing the adhesiveness of the resin by the pretreatment. In the method disclosed in JP-A-4-370123, a polymerizable monomer such as acrylic acid or methyl acrylate is brought into contact with a fluororesin, and when this is irradiated with an excimer laser, the monomer is graft-polymerized on the fluororesin surface. And to improve the adhesiveness of the fluororesin surface.
[0003]
[Problems to be solved by the invention]
However, in the treatment with a chemical solution such as dichromic acid, it is necessary to immerse the adhesive in the chemical solution, and it is difficult to selectively treat and bond the inside or outside of the tube, or a portion away from the tube opening end. In addition, since it is necessary to wash and dry the adhesive after performing the chemical treatment, the process up to bonding becomes extremely long. Furthermore, chemicals such as dichromic acid are very toxic and dangerous to the human body. In the corona discharge treatment, since an electrode is used, it is difficult to perform stable treatment and adhesion to a very thin tube. Further, in the method disclosed in JP-A-4-370123, a polymerizable monomer is indispensable, and a bonding step using an adhesive suitable for a modified surface is required by preparing a monomer suitable for an adhesive. It is.
[0004]
The present invention has been made in view of the problems of the prior art, and it is possible to simultaneously perform modification and adhesion, regardless of the position and diameter of the resin tube, and perform adhesion after modification. The purpose of the present invention is to provide a method for securely bonding a resin tube in which the adhesive strength is easily improved in a short time because the adhesive is not limited.
[0005]
[Means for Solving the Problems]
In order to achieve the above object, the present invention provides a method of bonding a resin tube for bonding a fluororesin tube having an inner wall and an outer wall to an object to be bonded, wherein at least one of an inner wall and an outer wall of the tube is connected to the outer wall. A step of interposing at least an adhesive between the adhesive and an adhesive; and irradiating an energy ray including a laser or ultraviolet light having a photon energy of 80 kcal / mol or more from at least one of the inside and the outside of the tube, And a step of chemically bonding an agent to the tube and bonding the tube to the resin tube.
Further, the present invention provides a method of bonding a resin tube for bonding a fluororesin tube having an inner wall and an outer wall and an object to be bonded, wherein at least one of the inner wall and the outer wall of the tube is the same as the fluororesin tube. A step of interposing at least a hydrogen-containing compound between the element having a side chain and an adherend having an element which is cut when irradiated with an energy ray having a photon energy of 80 kcal / mol or more, At least one of the inside and the outside of the tube is irradiated with an energy ray including a laser or ultraviolet light having a photon energy of 80 kcal / mol or more, and the hydrogen compound and the tube, or the tube and the adherend, are irradiated. Chemically bonding and bonding, a method of bonding a resin tube, comprising: Subjected to.
[0006]
Here, the resin tube is suitable for various materials such as fluororesin, PE, PP, PMMA, PET, and POM, and among them, fluororesin, PE, and PP are preferable. PTFE, FEP and ETFE are more preferable among fluororesins. However, materials other than these resins are not particularly limited. In addition, as the shape of the resin tube, other than the case where the cross section perpendicular to the axial direction is a circle, square, rectangle, polygons such as triangles, ellipses, and any other objects are possible. The present invention is also applicable to a shape having a notch.
[0007]
Ultraviolet light in the present invention refers to a wavelength of 300 nm or less, and an excimer laser using ArF, KrF, or XeCl is preferable. However, depending on the form of the adhesive, the irradiation with the absorption wavelength of the reaction initiator or the heat ray can be performed simultaneously or with a delay.
[0008]
As the adhesive in the present invention, an adhesive having any bonding form can be used. The adhesive in the present invention is, for example, an energy ray-curable adhesive such as an electron beam-curable type or an ultraviolet ray-curable type, or a thermosetting adhesive. Here, the energy ray-curable adhesive is not particularly limited, but specifically, an ultraviolet ray-curable adhesive mainly containing modified acrylate or methacrylate can be used. As the thermosetting adhesive, an epoxy-based, polyurethane-based, phenol-based, polyester-based adhesive or the like can be used, but an epoxy-based adhesive is particularly preferable. Further, a UV-curable adhesive having a thermosetting property, for example, a modified epoxy-acrylate-based adhesive is also applicable. In the present invention, the hydrogen-containing compound, specifically, organic acids containing hydrogen, hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, acetals, ketones, fatty acids, One or a mixture of acid anhydrides, esters, nitrogen compounds, sulfur compounds, or inorganic acids, inorganic base compounds, other inorganic hydrogen compounds, or compounds consisting of water, and derivatives thereof. Simultaneously with or after the irradiation with the energy beam, the adhesive or the compound is cured or chemically bonded.
[0009]
The adherend in the present invention is not particularly limited, but when using one or a mixture selected from hydrogen-containing compounds interposed between the resin tube and the adherend, the same as the resin tube is used. It is possible to use an adherend having an element in a side chain or an adherend from which an element in a side chain irradiated with an energy ray having a photon energy of 80 kcal / mol or more is cut. Applying pressure here is desirable because the resin can be made thinner and more uniform, and the resins can be close to each other at the level of several molecules of the hydrogen-containing compound. At this time, a liquid compound that is easily deformed by pressure is desirable as the hydrogen-containing compound.
[0010]
The method of applying pressure to the hydrogen-containing compound is not particularly limited as it is possible to use any method, for example, a method of fitting a member in the hydrogen-containing compound and applying a hydrostatic pressure as it is, Alternatively, the diameter of the portion where the hydrogen-containing compound is interposed, the inner diameter of the outer member is made smaller than the outer diameter of the inner member, and the fitting portion is shrunk, or the hydrogen-containing compound is interposed. A method of covering the heat-shrinkable tube from the outside of the site and shrinking the bonded portion by heating is used.
[0011]
The energy beam irradiating means is not particularly limited, but is preferably uniform irradiation to the bonding portion. For example, a means for rotating the tube around a center of gravity with respect to a cross section perpendicular to the axial direction, or a mirror or a lens Means for irradiating the tube while rotating the energy beam about the center of gravity with respect to a cross section perpendicular to the axial direction of the tube using an optical element such as Means for irradiating after guiding to an irradiation unit using a waveguide made of a halogen compound such as calcium iodide or an optical element may be considered. For short-time irradiation, a resin waveguide such as an amorphous fluororesin can be used. As the material of the waveguide, various materials can be used as long as the material transmits the energy rays, but it is particularly preferable to use synthetic quartz.
[0012]
[Action]
Hereinafter, the operation of the present invention will be described.
[0013]
When an energy ray containing ultraviolet light is irradiated with an adhesive or a compound containing hydrogen interposed between the resin tube and the adherend, the resin and the adhesive or the hydrogen-containing compound have a large absorption for ultraviolet light. Therefore, the element of the side chain in the molecular chain is selectively cut by the energy of the ultraviolet light. Normally, the cut and released elements stop the irradiation of the energy rays and combine again with the main chain skeleton. However, since the resin tube and the adhesive or the hydrogen-containing compound are in contact with each other, they are bonded in a more stable state without re-bonding, and the resin and the adhesive or the hydrogen-containing compound are chemically bonded. For example, if the resin tube is made of PTFE, when ultraviolet light is irradiated, the CF bond existing in the PTFE is dissociated by the energy of the ultraviolet light (CF bond dissociation energy 128 kcal / mol), and F is released. In addition, hydrogen (H) of C—H bond existing in the adhesive is also released (C—H bond dissociation energy: 80.4 kcal / mol). Then, hydrogen and fluorine combine to form HF. Furthermore, carbon (C) of PTFE and carbon of the adhesive bond to form a carbon bond (CC bond). At this time, since the absorption band of ultraviolet light of HF is very short at 161 nm or less, there is no possibility of dissociation, and there is a low possibility that fluorine takes a CF bond again.
[0014]
In particular, the following characteristic actions occur by selecting the means.
[0015]
The bond dissociation is achieved by using energy rays having high photon energy as energy rays, particularly ArF excimer laser light (148 kcal / mol), KrF excimer laser light (114 kcal / mol), and XeCl excimer laser light (92.2 kcal / mol). Even with a resin having high energy, it is possible to easily break the bond between molecules.
[0016]
When an energy ray-curable adhesive is used as the adhesive, it is possible to chemically bond the resin tube and the adhesive by irradiating ultraviolet light, and to simultaneously cure the adhesive. In addition, by using a thermosetting adhesive, by heating while irradiating energy rays, it is possible to simultaneously perform chemical bonding between the resin tube and the adhesive and curing of the adhesive. When a fast-curing adhesive is used, it is desirable to apply visible light, electron beam, and heat with a delay.
[0017]
When the adherend has, in the side chain, the same element as the resin tube or an element that is cut when irradiated with an energy ray having a photon energy of 80 kcal / mol or more, a hydrogen-containing compound is used as an adhesive, By applying a pressure to the hydrogen-containing compound to form a very thin layer, and in a state where the distance between the resin tube and the object to be bonded is close to several molecular levels, DF, Elements such as fluorine and hydrogen present in the C—H bond are cut off, and HF and H ₂ Form and stabilize. Then, the main chains from which the elements have been separated are connected to each other, so that the tube and the adherend can be bonded to each other.
[0018]
Furthermore, the energy ray is guided by using an optical element such as a glass waveguide, a resin waveguide, or a halide waveguide, or an optical element such as a mirror or a lens. It is possible to adhere uniformly over the entire circumference of the tube without damping or deterioration. In particular, when bonding a resin or a metal which does not transmit ultraviolet light to the outer wall of the tube, the energy beam is guided into the tube by the above-described method, and the tube is irradiated with the energy beam, thereby enabling the bonding.
[0019]
【Example】
(First embodiment)
(Constitution)
A first embodiment of the present invention will be described with reference to FIGS.
[0020]
In FIG. 5, reference numeral 1 denotes an ArF excimer laser. Reference numeral 14 denotes a synthetic quartz waveguide having a diameter of 2.5 mm. The waveguide 14 has a rotation and axial movement mechanism. Reference numeral 19 denotes a sample in which an adherend, water, and a tube are combined, and is fitted to the waveguide 14. FIG. 6 is an enlarged sectional view of a fitting portion between the sample 19 and the waveguide 14. Reference numeral 7 denotes an optical path of the excimer laser light in the waveguide 14. Reference numeral 16 denotes a tube made of FEP having an inner diameter of 3.0 mm and an outer diameter of 13.0 mm, and reference numeral 18 denotes a tube made of FEP having an inner diameter of 2.5 mm and an outer diameter of 3.1 mm. Since the FEP tube 16 is as thick as 5 mm, the laser light is absorbed, and the amount of light reaching the surface to be bonded is small. The fitting length between the FEP tube 16 and the FEP tube 18 is 30 mm, and water 17 is interposed in the fitting portion as a hydrogen compound. The bonding portion is 10 mm from 20 mm away from the tip of the FEP tube to 30 mm. The sample 19 was constituted by fitting the FEP tube 16 and the FEP tube 18 in water. Further, since the fitting between the FEP tube 16 and the FEP tube 18 is a shrink fit, the water 17 is under pressure. Further, the tip 20 of the waveguide 14 is a plane that forms an angle of 45 ° with respect to the axis, and is provided with a mirror that reflects excimer laser light. The waveguide 14 is repeatedly moved three times in the axial direction by 2.5 mm every five minutes by a moving mechanism three times to irradiate a total of 10 mm. Also, it is rotated at 2 rpm by a rotation mechanism. Laser irradiation condition is energy density 50mJ / cm ² 3000 shots were repeated four times at a repetition rate of 10 pps in accordance with the movement of the waveguide.
[0021]
(Action)
The laser light emitted from the ArF excimer laser device 1 passes through the waveguide 14 like the optical path 7 and is reflected by a mirror provided at the tip 20 of the waveguide 14. The reflected laser light is transmitted while being absorbed by the FEP tube 18 and the water 17 and reaches the FEP tube 16 from the inner surface. At this time, since the waveguide 14 is rotating, the laser light is irradiated over the entire circumference of the tube. Further, the waveguide is moved in the axial direction by the moving mechanism, and a length of 10 mm is irradiated. The following reaction occurs at the interface between the inner wall of the tube 16 and the water 17 and at the interface between the outer wall of the tube 18 and the water 17. The laser beam breaks the CF bond on the surfaces of the tubes 16 and 18 to release F. The liberated F combines with H in water to form HF. On the other hand, the carbon in the tubes 16 and 18 forms an ether bond (CO-C bond) or a direct carbon bond (CC bond) via oxygen in water, and the tubes 16 and 18 are bonded to each other. .
[0022]
Analysis was performed by X-ray photoelectron spectroscopy (XPS) in order to confirm the operation in this example. For the analysis, the sample was cut open, and the bonded portion was peeled off. The results are shown in FIGS. FIG. 11 shows the distribution of the binding energy before the laser irradiation, and FIG. 12 shows the distribution after the laser irradiation. As can be seen from the XPS chart, since the CF bond is reduced on the FEP surface and the CO bond is formed, defluorination (F) is performed and oxygen (O) is introduced. You can check.
[0023]
(effect)
In order to confirm the effect, the bonded sample was held in a tensile tester by a chuck and pulled in a vertical direction, and the bonding strength at that time was determined. The tensile adhesion test was performed in the same manner as in the second and subsequent examples. In addition, a tensile adhesion test was performed for a product bonded by using the same method without irradiating a laser. The same applies to the second and subsequent embodiments. Table 1 shows the results of the tensile adhesion test. Naturally, adhesion cannot be achieved without laser irradiation, but by using the present invention, an adhesion strength of 3.89 kgf / cm was obtained.
[0024]
In this embodiment, since water is used as the adhesive, it is not necessary to prepare an adhesive separately, and it is not necessary to cure the adhesive, so that the bonding method is very simple.
[0025]
Further, in the present embodiment, the portion from 20 mm to 30 mm from the opening end of the tube 18 is bonded, but the bonding portion is set arbitrarily at the opening end, at a position away from the opening end, or intermittently. It is possible.
[0026]
In this example, similar effects were obtained even when a halogen compound or an amorphous fluororesin was used for the waveguide.
[0027]
(Second embodiment)
(Constitution)
A second embodiment of the present invention will be described with reference to FIGS.
[0028]
In FIG. 1, reference numeral 1 denotes an ArF excimer laser device, 2 denotes a light guide device, 3 denotes a sample in which a resin tube, an object to be bonded, and an adhesive are combined, and 7 denotes an optical path of the excimer laser light. FIG. 2 is an enlarged sectional view of Sample 3 in FIG. 4 is a resin tube, 5 is an adherend, and 6 is an adhesive. In the second embodiment, PTFE was used for the fluororesin tube 4, SUS304 round bar was used for the adherend 5, and thermosetting epoxy adhesive was used for the adhesive 6. The laser irradiation conditions are as follows: energy density 50 mJ / cm ² The number of repetitions was 600 shots at 10 pps, and irradiation was performed once under the above-mentioned conditions, then rotated 180 ° about the axis, and again irradiated under the same conditions. Thereafter, Sample 3 was put into an oven, and the adhesive was cured at 80 ° C. for 15 hours.
[0029]
(Action)
Laser light emitted from the excimer laser device 1 passes through the optical path 7 and is guided to the sample 3 by a mirror. The excimer laser light that has reached the sample 3 reaches the adhesive 6 while being absorbed by the fluororesin tube 4. The laser beam that has reached the tube 4 and the adhesive 6 breaks the C—F bond and forms HF at the interface between the tube 4 and the adhesive 6, and the tube 4 and the adhesive 6 are bonded to the C—C bond. To form a chemical bond. After that, the adhesive is cured, so that the tube 4 and the adherend 5 are adhered through the adhesive 6.
[0030]
(effect)
Table 1 shows the tensile adhesive strength. As a result of the tensile test, the sample irradiated with the laser beam did not break at the bonding portion, but the material was broken such that the tube was cut. In this example, the stronger the bonding strength was than the strength of the tube itself, the stronger the bonding was performed. An improvement in the adhesive strength can be confirmed even when compared with a sample not irradiated with laser light.
[0031]
(Third embodiment)
(Constitution)
The third embodiment of the present invention has been described with reference to FIGS.
[0032]
In FIG. 3, 1 is an ArF excimer laser device, 7 is a laser beam path, 3 is a sample in which an adhesive, a resin tube, and an object are combined, and 12 is a laser beam rotating irradiation device. Also, 12 is contained in a heating device 13. An enlarged view of Sample 3 is shown in FIG. Reference numeral 4 denotes a tube made of FEP, reference numeral 5 denotes an adherend of a SUS304 round bar, and reference numeral 6 denotes a thermosetting imparting type ultraviolet curable adhesive. FIG. 4 is an enlarged view of the laser beam rotary irradiation device 12. The laser beam rotating irradiation device 12 has a rotatable cylindrical body, and a mirror 9 for guiding the laser beam is fixed inside the laser beam irradiation device 12. 7 is a laser beam path, and 12 is rotated at 10 rpm. Sample 3 is fixed at twelve centers of rotation.
[0033]
31 Is a mercury ultraviolet lamp light source for curing the adhesive 6, and is applied to the bonded portion of the sample 3.
[0034]
Laser irradiation condition is energy density 100mJ / cm ² 6,000 shots at a repetition rate of 10 pps. The inside of the heating device is kept at 100 ° C.
[0035]
(Action)
The laser light emitted from the excimer laser device 1 enters the heating device 13 and is guided into the irradiation device 12 as it is. The laser light guided into the irradiation device is reflected by the mirror 9 and irradiates the sample 3 through the optical path 7. Here, since 12 is rotating, the laser light guided by the mirror fixed to 12 also rotates around the sample 3. Therefore, the laser light is uniformly irradiated over the entire circumference of the sample 3. The same operation as in the second embodiment occurs in the sample 3 irradiated with the laser light, and the tube 4 and the adhesive 6 are chemically bonded. In addition, since an ultraviolet-curing adhesive with thermosetting properties is used for the adhesive, polymerization is started by ultraviolet light or excimer laser light irradiated simultaneously with the laser, and heat is applied by a heating device. Thereby, the adhesive is cured.
[0036]
(effect)
As shown in Table 1, similar to the second example, an improvement in the adhesive strength is observed.
[0037]
Further, in this embodiment, since the laser beam is rotated, stable bonding can be performed over the entire circumference of the tube. Further, since the chemical bonding between the tube and the adhesive and the curing of the adhesive can be performed at the same time, the bonding step can be shortened.
[0038]
In this example, an ultraviolet-curable adhesive having thermosetting properties was used as an adhesive, but an ultraviolet-curing adhesive having no thermosetting properties, an electron beam-curing adhesive or a thermosetting adhesive having no thermosetting properties was used as the adhesive. Similar curing was obtained using a curable adhesive. When an ultraviolet-curable adhesive having no thermosetting property is used, the heating device 13 becomes unnecessary.
[0039]
(Fourth embodiment)
(Constitution)
A fourth embodiment of the present invention will be described with reference to FIGS.
[0040]
14 is the same as in the first embodiment. Reference numeral 1 denotes a KrF excimer laser device. Reference numeral 19 denotes a sample in which a PE tube, an adhesive, and an adherend are combined. FIG. 6 is an enlarged sectional view of a fitting portion between the sample 19 and the waveguide 14. 7 and 14 are the same as in the first embodiment. Reference numeral 16 denotes a SUS303 pipe having an inner diameter of 3.2 mm. Reference numeral 18 denotes a PE tube having an outer diameter of 3.0 mm and an inner diameter of 2.5 mm. A two-component epoxy adhesive 17 is applied between the pipe 16 and the tube 18. Laser irradiation conditions and waveguide moving conditions are the same as in the first embodiment. Thereafter, the adhesive was left at room temperature for 24 hours to cure the adhesive.
[0041]
(Action)
As in the first embodiment, the laser light passing through the optical path 7 reaches the adhesive 17 while being absorbed by the tube 18. At the interface between the tube 18 and the adhesive 17, the C—H bond on the surface of the tube 18 is broken and H is released. The released H is combined with H in the adhesive to form H ₂ To form On the other hand, C from which H is released is bonded to C in the adhesive, and the surface of the tube 18 is chemically bonded to the adhesive. Thereafter, the tube 18 and the pipe 16 are bonded via the adhesive 17 by curing the adhesive.
[0042]
(effect)
As shown in Table 1, improvement in the adhesive strength is observed.
[0043]
Further, even when laser light cannot be irradiated from the outside as in the present embodiment, simple adhesion can be achieved by irradiating from the inside using a waveguide.
[0044]
If the tip 20 of the waveguide 14 is shaped as shown in FIG. 7A, the laser beam passes through the optical path 7 and is uniformly emitted from the entire circumference of the waveguide 14. Alternatively, in FIG. 7B, the optical path 7 is refracted by shaping the distal end 20 of the waveguide 14 into a conical shape, and the laser light is applied to the entire circumference of the tube. In this case, a rotating mechanism is unnecessary.
[0045]
(Fifth embodiment)
(Constitution)
A fifth embodiment of the present invention will be described with reference to FIGS.
[0046]
In FIG. 8, 1 is an ArF excimer laser device, 27 is a heating device, 22 is a synthetic quartz pipe waveguide having an inner diameter of 3.5 mm and a thickness of 5 mm, and the waveguide 22 is provided with a moving mechanism in the axial direction. Reference numeral 23 denotes a sample in which a tube, an adhesive, and an adherend are combined. FIG. 9 is an enlarged sectional view of a fitting portion between the sample 23 and the waveguide 22. The tip of the waveguide 22 is a mirror 28. 7 is the optical path of the laser beam, 26 is Route It is a tube made of PP with an inner diameter of 2.5 mm and an outer diameter of 3.5 mm. 25 is a 2.2 mm piano wire. A thermosetting one-liquid addition type silicone adhesive 24 is applied between the tube 26 and the piano wire 25. The waveguide 22 and the PP tube 26 are fitted. Laser irradiation condition is energy density 50mJ / cm ² 6,000 shots at a repetition rate of 10 pps. The waveguide 22 reciprocates at a rate of 5 mm / sec and an amplitude of 5 mm by the moving mechanism. The inside of the heating device 27 is maintained at 120 ° C.
[0047]
(Action)
The laser light emitted from the laser device 1 passes through the optical path 7 and is reflected by the mirror 28, reaches the adhesive 24 while being partially absorbed by the tube 26, and is absorbed. The same operation as in the second embodiment occurs at the interface between the tube 26 and the adhesive 24, and the tube 26 and the adhesive 24 are chemically bonded over 10 mm by reciprocating the waveguide 22. At the same time, the adhesive is heated at 120 ° C. by the heating device, so that the curing of the adhesive 24 proceeds. After the laser irradiation, the adhesive is completely cured by heating for further 3 hours, and the tube 26 and the piano wire 25 are bonded via the adhesive 24.
[0048]
(effect)
As shown in Table 1, the adhesive strength is improved.
[0049]
In addition, the use of the pipe-shaped waveguide makes it possible to bond the entire circumference of the tube at once and uniformly.
[0050]
(Sixth embodiment)
(Constitution)
A sixth embodiment of the present invention will be described with reference to FIGS.
[0051]
In FIG. 1, 1, 2, 3, and 7 are the same as in the second embodiment. The sample 3 can be rotated and moved in the axial direction by a motor. FIG. 2 shows a cross section of Sample 3. 4 is a PTFE tube having an inner diameter of 300 mm, and 5 is a SUS pipe having an outer diameter of 296 mm. An ultraviolet curable adhesive TR3102 (manufactured by Three Bond Co., Ltd.) is applied between the tube 4 and the pipe 5. The laser irradiation conditions were the same as in the third embodiment, and the irradiation area was 20 mm in the tube axis direction and 10 mm in the direction perpendicular to the axis. Sample 3 is rotated at 10 rpm by a motor.
[0052]
(Action)
The tube 4 and the pipe 5 are chemically bonded by the same operation as in the second embodiment. Further, since the adhesive 6 is of an ultraviolet curing type, the curing of the adhesive also proceeds at the same time. Furthermore, since the sample is rotating, the tube 4 and the pipe 5 are bonded over the entire circumference.
[0053]
(effect)
As shown in Table 1, the adhesive strength is improved. In this example, since the bonding area was large, the bonding strength per unit area was determined.
[0054]
In this embodiment, since the tube diameter is large, it is difficult to rotate the optical element as in the third embodiment. However, by rotating the sample, uniform bonding can be achieved over the entire circumference of the tube regardless of the tube diameter.
[0055]
(Seventh embodiment)
(Constitution)
A seventh embodiment according to the present invention will be described with reference to FIGS.
[0056]
8 and 9, 1, 7, 23, 24, 25, 26, 27, and 28 are the same as those in the fifth embodiment, and 22 is a hollow pipe-shaped waveguide formed by molding an amorphous fluororesin. FIG. 10 shows an enlarged cross-sectional view of the waveguide 22. The waveguide 22 has a pipe shape as in the fifth embodiment, but has a hollow structure in this embodiment, and the hollow portion 29 is filled with nitrogen. Most of the optical path 7 passes through the nitrogen in the hollow portion 29.
[0057]
(Action)
The same operation as in the fifth embodiment occurs. Further, in this embodiment, since the laser light passes through nitrogen, the attenuation of the laser light is smaller than that in air or through synthetic quartz.
[0058]
(effect)
As shown in Table 1, the adhesive strength is improved. In addition, uniform bonding became possible as in the fifth embodiment.
[0059]
Further, since the laser light is largely absorbed by oxygen, the deterioration and attenuation of the laser light increase when the optical path from the radiation part to the irradiation part is 1 m or more in the atmosphere. Even if the optical path becomes longer due to the filling, the laser beam can be irradiated without deterioration and attenuation.
[0060]
[Table 1]

[0061]
【The invention's effect】
As described above, the present invention is capable of performing modification and bonding simultaneously regardless of the diameter and the site of the tube, and also does not limit the adhesive when performing the bonding after the modification. This is a safe method of bonding a resin tube in a short time, in which the bonding strength is easily improved and a substance which has a bad effect on the human body is not used.
[Brief description of the drawings]
FIG. 1 is a perspective view of an apparatus for performing the method of the present invention.
FIG. 2 is an enlarged sectional view showing a part of the apparatus shown in FIG. 1;
FIG. 3 is a perspective view of another apparatus for performing the method of the present invention.
FIG. 4 is an explanatory view showing a part of the apparatus of FIG. 3 in an enlarged manner.
FIG. 5 is a perspective view of another apparatus for performing the method of the present invention.
FIG. 6 is an enlarged sectional view showing a part of the apparatus shown in FIG. 5;
FIG. 7 is an explanatory view schematically showing a part of the apparatus shown in FIG. 6;
FIG. 8 is a perspective view of another apparatus for performing the method of the present invention.
FIG. 9 is an enlarged sectional view showing a part of the apparatus shown in FIG. 8;
FIG. 10 is an enlarged sectional view showing a part of the apparatus shown in FIG. 8;
[FIG. 11] X-ray photoelectron analysis is performed, X-rays are incident on a sample, and photoelectrons bounced from the sample are counted by a detector. From the count amount, it is possible to determine what binding energy the sample has. FIG. 3 is a diagram showing an energy distribution before laser irradiation in this case.
FIG. 12 is a diagram corresponding to FIG. 11, and particularly a diagram showing an energy distribution after laser irradiation.
[Explanation of symbols]
1 ArF excimer laser, 4 resin tube, 5 adherend, 6 adhesive, 14 waveguide, 19 sample, 22 waveguide, 23 sample, 27 heating device.

Claims (13)

In a method for bonding a resin tube for bonding a fluororesin tube having both an inner wall and an outer wall and an object to be bonded,
A step of interposing at least an adhesive between at least one of the inner wall and the outer wall of the tube and the adherend,
A step of irradiating an energy ray containing a laser or ultraviolet light having a photon energy of 80 kcal / mol or more from at least one of the inside and the outside of the tube, chemically bonding the adhesive to the tube, and bonding the tube;
A method of bonding a resin tube, comprising: The adhesive is an energy ray-curable type or a heat-curable type, and is irradiated with a specific wavelength or heat at the start of polymerization at the time of energy ray irradiation, or simultaneously or with a delay to cure the adhesive. The method for bonding a resin tube according to claim 1, wherein: 3. The method according to claim 1, wherein the adhesive is a liquid adhesive. The method for bonding a resin tube according to any one of claims 1 to 3, wherein the energy ray is irradiated while pressure is applied to the adhesive. In a method for bonding a resin tube for bonding a fluororesin tube having both an inner wall and an outer wall and an object to be bonded,
At least one of the inner wall and the outer wall of the tube and the side chain having the same element as the fluororesin tube or an element which is cut when irradiated with an energy ray having a photon energy of 80 kcal / mol or more. Between the adherend, at least a step of interposing a hydrogen-containing compound,
At least one of the inside and the outside of the tube is irradiated with an energy ray including a laser or ultraviolet light having a photon energy of 80 kcal / mol or more, and the hydrogen compound and the tube, or the tube and the adherend, are irradiated. Chemically bonding and bonding,
A method of bonding a resin tube, comprising: The hydrogen-containing compound is an organic acid containing hydrogen, a hydrocarbon, a halogenated hydrocarbon, an alcohol, a phenol, an ether, an acetal, a ketone, a fatty acid, an acid anhydride, an ester, or nitrogen. 6. A compound or sulfur compound, or one or a mixture selected from inorganic acids, inorganic base compounds, other inorganic hydrogen compounds, and compounds composed of water, and derivatives thereof. Method for bonding resin tubes. The method for bonding a resin tube according to claim 5 or 6, wherein the hydrogen-containing compound is a liquid compound. The method for bonding a resin tube according to any one of claims 5 to 7, wherein the energy ray is irradiated while applying pressure to the hydrogen-containing compound. The energy ray is at least one kind of energy ray selected from an ArF excimer laser, a KrF excimer laser, a XeCl excimer laser, a harmonic wave of a solid, gas, or dye laser, or an ultraviolet lamp. The method for bonding a resin tube according to any one of claims 1 to 8. 10. The energy beam is emitted from at least one of the inside and the outside of the tube while rotating the tube around a center of gravity with respect to a cross section perpendicular to the axial direction of the tube. 2. The method for bonding a resin tube according to claim 1. The method according to any one of claims 1 to 9, wherein at least one of the inside and the outside of the tube is irradiated with the energy beam while rotating the energy beam around a center of gravity with respect to a cross section perpendicular to the axial direction of the tube. 3. The method for bonding a resin tube according to claim 1. The method of bonding a resin tube according to any one of claims 1 to 11, wherein the energy ray is irradiated using a waveguide through which the energy ray is transmitted. The method according to claim 12, wherein the waveguide is made of synthetic quartz, UV glass, a halogen compound or a halogenated derivative.

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