WO2011071036A1 - Procédé d'adhésion d'élément et composite polymère - Google Patents

Procédé d'adhésion d'élément et composite polymère Download PDF

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WO2011071036A1
WO2011071036A1 PCT/JP2010/071891 JP2010071891W WO2011071036A1 WO 2011071036 A1 WO2011071036 A1 WO 2011071036A1 JP 2010071891 W JP2010071891 W JP 2010071891W WO 2011071036 A1 WO2011071036 A1 WO 2011071036A1
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Prior art keywords
graft chain
substrate
polycation
zwitterion
polyanion
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PCT/JP2010/071891
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English (en)
Japanese (ja)
Inventor
淳 高原
元康 小林
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独立行政法人科学技術振興機構
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Priority to JP2011545211A priority Critical patent/JP5613882B2/ja
Publication of WO2011071036A1 publication Critical patent/WO2011071036A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined

Definitions

  • the present invention relates to a method for adhering members, and more particularly, to a method for adhering members obtained by grafting polymer chains to the surfaces of two members, and a polymer composite obtained by this method.
  • the present invention relates to a method for adhering a member having a polycation-containing graft chain formed on the surface and a member having a polyanion-containing graft chain formed on the surface.
  • Non-patent Document 1 As a thin adhesive layer, it is known that an acrylamide polymer nanosheet prepared by Langmuir Blodgett can be used as an adhesive layer, and copper wiring can be prepared by electroless plating (Non-patent Document 1). However, little is known about adhesive layers with nanometer thickness. In general, non-equilibrium phenomena such as polymer interface adhesion, delamination, wetting, adsorption / desorption mechanism, and dynamic interfacial energy are very important for material development according to applications and specifications. There are many unclear points, and the clarification is urgently needed. *
  • Non-Patent Document 2 an “alternate adsorption method” was developed in which a thin film was formed using an aqueous solution of a polymer electrolyte (Patent Document 1) (Non-Patent Document 2) (Non-Patent Document 3). Since this report, it has been shown that it can be applied not only to polymer electrolytes but also to neutral polymers, nanoparticles, colloids, proteins and clay compounds.
  • the “alternate adsorption method” is characterized by the ability to control the film thickness at the nanometer level, the degree of freedom of constituent materials, the degree of freedom of bonding available, and the like. Moreover, it is used as a surface design technique for controlling the adsorptivity of cells and proteins to the surface of a biomaterial (Non-patent Document 4).
  • Non-patent document 5 When polycation and polyanion, which are polyelectrolytes, are mixed, both adsorb due to strong electrostatic interaction to form a polyion complex. Therefore, when the substrate surface coated with polycation and the substrate surface coated with polyanion are brought into contact with each other, they are easily bonded together (Non-patent document 5) (Non-patent document 6) (Non-patent document 7) (Non-patent document). 8). However, depending on the type of the substrate, sufficient adhesion performance cannot be obtained because the coating film is peeled off from the substrate surface due to the influence of water and moisture.
  • the target base materials are limited to materials having a high affinity with polymer electrolytes such as biological membranes and proteins, and it is difficult to develop a wide range of engineering materials.
  • Neoh et al. Attempted to bond polymer films by a method using surface plasma polymerization, but in order to produce members by free radical polymerization using light or heat, the molecular weight and molecular weight distribution of the graft chain In addition, since the control of the film thickness is not sufficient, inclusion of a low molecular weight polymer component, breakage at the polymer interface during peeling, etc.
  • Patent Document 2 Non-Patent Document 9
  • Non-Patent Document 10 Non-patent document 11
  • Non-patent document 12 Non-patent document 12
  • non-patent document 13 Non-patent document 14
  • non-patent document 15 non-patent document 16
  • Neoh et al. Macromolecules, 30, 3354-3362 (1997).
  • K. G. Neoh et al. Journal of Polymer Science: Part A: Polymer Chemistry, 36, 357-366 (1998) K. G. Neoh et al. , Langmuir, 14, 921-927 (1998) K. G. Neoh et al. , Polymer, 39, 2429-2436 (1997) K. G. Neoh et al. , Journal of Polymer Science: Part A: Polymer Chemistry, 36, 31 07-3114 (1998) K. G. Neoh et al. , Journal of Applied Polymer Science, 70, 1977-1983 (1998). K. G. Neoh et al.
  • the present inventor has found that the above problem can be solved by using two members in which polymer graft chain layers having different polarities including an electrolyte structure are formed on the adhesion surface.
  • the polymer graft layer defined in the present invention is a nanometer-order thin film formed by covalently bonding a polymer chain end or a part of a polymer chain to a substrate surface. Therefore, the polymer graft layer is not peeled off from the substrate surface by washing with a solvent or slight friction. Therefore, the present invention does not cause cohesive failure or adhesive residue of the adhesive layer on the surface of the adherend, which is a problem in general adhesion methods, and adhesion and peeling without damaging the adherend when peeling the adherend. It is an object of the present invention to provide a composite comprising an extremely thin adhesive layer and an adhesive layer that can be repeated.
  • the novel adhesive member has a strong adhesive performance.
  • the polycation-containing polymer graft chain having a positive charge includes an ammonium group (Non-patent Document 5).
  • Examples of negatively charged polyanion-containing polymer graft chains include those having a sulfonic acid group (Non-Patent Document 6) and those having a carboxyl group (Non-Patent Document 7) (Non-Patent Document 8).
  • the ion-containing polymer graft chain include carbobetaine, phosphobetaine, and sulfobetaine.
  • Graft chains are opposed to each other with a first member having a polycation or zwitterion-containing graft chain formed on the surface and a second member having a polyanion or zwitterion-containing graft chain formed on the surface.
  • a method for bonding members to be bonded includes the following matters as a summary.
  • the polycation-containing graft chain is selected from a graft chain having a pyridinium group or an ammonium group, and the polyanion-containing graft chain is a graft chain having a carboxyl group, a sulfonic acid group, a sulfate group, or a phosphate group.
  • the method according to (1) or (2), wherein the zwitterion-containing polymer graft chain is selected from graft chains having carbobetaine, phosphobetaine, sulfobetaine and the like.
  • the polycation or zwitterion-containing graft chain and the polyanion or zwitterion-containing graft chain are fixed to the first member and the second member via covalent bonds, respectively (1) to ( The method according to any one of 4).
  • the graft member faces the first member having a polycation or zwitterion-containing graft chain formed on the surface and the second member having a polyanion or zwitterion-containing graft chain formed on the surface.
  • the present invention there is provided a technique for bonding a first member having a polycation-containing graft chain formed on the surface and a second member having a polyanion-containing graft chain formed on the surface. That is, since the present invention shows adhesion only to substances having different polarities, only specific members and parts can be selectively bonded.
  • the first member and the second member are bonded by interposing a very small amount of water droplets between the bonding interfaces, so that the surrounding environment is contaminated. And a technology with an extremely low environmental load is provided.
  • FIG. 1 is a schematic view of a tensile tester used for evaluating the adhesive strength in Examples of the present application.
  • FIG. 2 is a schematic view showing a method for bonding members in the embodiment of the present application.
  • FIG. 3 is a schematic view of a tensile tester used for evaluating the adhesive strength.
  • FIG. 4 is a schematic view of a test apparatus for evaluating the holding force when a static load is applied in a direction parallel to the bonding site.
  • FIG. 5 is a diagram of measurement results when evaluation by X-ray photoelectron spectroscopy (XPS) is performed in order to observe the member surface before and after peeling.
  • FIG. 6 is a photograph when observed with an atomic force microscope (AFM) to observe the peeled member surface.
  • XPS X-ray photoelectron spectroscopy
  • a first member having a polycation-containing graft chain formed on the surface and a second member having a polyanion-containing graft chain formed on the surface are bonded to each other with the graft chains facing each other.
  • the polykatine-containing graft chain and the polyanion-containing graft chain used in the present invention are polymers having functional groups having different polarities in the main chain or side chain.
  • the graft chain is not limited to one composed of a single monomer, and may be composed of two or more types of monomers.
  • the polyanion generally has a negatively charged functional group such as sulfonic acid, sulfuric acid, carboxylic acid, phosphoric acid, such as polystyrene sulfonic acid, polyvinyl sulfate, dextran sulfate, chondroitin sulfate, poly (3-methacryloyl) Propyl phosphoric acid), poly (oligoethylene glycol phosphate), hyaluronic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyfumaric acid, poly (2-acrylamido-2-methyl-1-propanesulfonic acid), etc.
  • PSPM poly (3-sulfopropyl methacrylate)
  • PMANA polymethacrylic acid sodium salt
  • the polycation generally has a positively charged functional group such as pyridinium group, ammonium group, quaternary ammonium group, amino group, such as polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammonium chloride, Polyvinylpyridine, poly (N-methyl-2-vinylpyridine), poly (N-methyl-4-vinylpyridine), polylysine, polystyrenemethylenediethylmethylamine, poly (dimethylaminoethyl methacrylate), poly (2-methacryloyl) Oxyethyldimethylammonium iodide), and preferably poly (2-methacryloyloxydimethylammonium chloride) (PMTAC) can be used.
  • a positively charged functional group such as pyridinium group, ammonium group, quaternary ammonium group, amino group, such as polyethyleneimine, polyallylamine hydrochloride, polydiallyldimethylammoni
  • the combination of the polyanion and the polycation is preferably a combination of PSPM, which is a polyanion, and PMTAC, which is a polycation.
  • One end of each of the polycation and the polyanion is immobilized (grafted) with the first member and the second member by a covalent bond, respectively.
  • the surface of the member is made of BHE (2-bromo-2-methylpropyloxyhexyltrioxysiloxane) (or 2-bromo-2-methylpropylene-2-methylpropylenesiloxane (BHM), 2-hydroxy-2-hydroxypropylene (2-Homopropylenesiloxane) 2 ′, 2 ′, 6 ′, 6′-tetramethylpiperidine-1′-oxy) -2-phenyl-ethylphosphonic acid, etc.) and the like to share the site that is the starting point of polymerization on the surface of the member By surface-initiated polymerization using this site as a starting point.
  • BHE 2-bromo-2-methylpropyloxyhexyltrioxysiloxane
  • BHM 2-bromo-2-methylpropylene-2-methylpropylenesiloxane
  • 2-Homopropylenesiloxane 2-Homopropylenesiloxane
  • polycation-containing graft chains or member polyanion containing graft chains are firmly bonded can be obtained on the surface. Therefore, in the present invention, since the polyanion-containing graft chain end and the polycation-containing graft chain end are covalently bonded to the member surface via the surface initiator, the first member and the second member are peeled off. It is firmly fixed without doing.
  • first member having the polycation graft layer thus obtained and the second member having the polyanion graft layer are bonded to each other, strong electrostatic interaction is exerted between both graft layers, and this causes the members to adhere to each other. To do.
  • the essential adhesive layer is a polyelectrolyte graft layer.
  • the adhesive layer is a polymer electrolyte laminated film in which polycations and polyanions are alternately laminated, but the laminated film and the surface of the member that is the adherend are not chemically bonded.
  • the adhesive layer is easily peeled from the member, and the once peeled adhesive layer cannot be reused.
  • the thickness of the polycation-containing graft chain and the polyanion-containing graft chain formed by the surface-initiated polymerization method is in the range of 1 to 1000 nm.
  • the first member having the polycation-containing graft chain formed on the surface and the second member having the polyanion-containing graft chain formed on the surface are bonded with water interposed, and then heated. Alternatively, it can be peeled off by treatment with a salt solution. In the present invention, peeling can be performed without causing breakage of the polymer chain during peeling by peeling by heating or treatment with a salt solution.
  • the peeled first member and the second member can be re-adhered with water interposed therebetween.
  • the material of the first member and the second member in the present invention is not particularly limited as long as the polymerization initiation site can be introduced by the surface treatment agent.
  • a metal substrate, a silicon substrate, a quartz substrate, fluorine Polymers such as polyethylene, polypropylene, and cellulose are preferred.
  • These shapes are not particularly limited, and can be applied to any surface such as a flat surface, a spherical surface, a columnar surface, and an inner wall of a hollow tube. These surfaces may have irregularities.
  • SPMK 3-sulfopropyl meth
  • the reaction was carried out at C for 15 hours to form a graft chain of MTAC polymer (PMTAC), which is a polycation, on a silicon substrate.
  • the reaction solution was red and uniform throughout.
  • the obtained PMTAC substrate was washed with water using a Soxhlet extractor, dried, and then confirmed to have a thickness of about 130 nm by an ellipsometer.
  • a tensile tester EZ-Graph manufactured by Shimadzu Corp.
  • the sample was installed by covering the air chuck with Kimwipe and fixing the silicon substrate.
  • the shearing force obtained by standardizing the force (N) detected in the load cell to the force per 1 cm 2 from the actual adhesion area was found, it was 38 N in the combination of PSPMK and PMTAC.
  • Example 1-4 BHE-immobilized silicon substrate (10 ⁇ 40 ⁇ 0.5 mm 3 ), CuBr (0.025 mmol), 4,4′-dimethyl-2,2′-bipyridil (0.050 mmol), isopropanol (3 mL) on a ⁇ 16 mm glass tube Then, water (5.0 mL) and 80 mL of 80% MTAC aqueous solution were sequentially added, freeze degassed, and reacted at 30 ° C. for 24 hours. The obtained substrate was washed with water using a Soxhlet extractor and dried. The film thickness of the PMTAC graft chain was confirmed to be about 210 nm by an ellipsometer.
  • a load cell of 100N specification was used, and the vertical pulling speed was 1 mm / min.
  • an aluminum plate (10 ⁇ 25 ⁇ 0.3 mm 3 ) was attached to both ends of the adhesive member as shown in FIG. 3, and this was fixed to an air chuck of a tensile tester.
  • the shearing force obtained by standardizing the force (N) detected in the load cell to the force per 1 cm 2 from the measured adhesion area was found, it was 84 N in the combination of PSPMK and PMTAC.
  • Example 1-6 When the PSPMK grafted silicon substrate (first member) prepared in Example 1-1 and the PMTAC grafted silicon substrate (second member) prepared in Example 1-4 were bonded together, the shear force per 1 cm 2 of the adhesion area was It was 80.0N. When 2 ⁇ L of water was dropped on the peeled member and the 10 mm portion of the substrate was bonded again, the two members were bonded together, and the shearing force per 1 cm 2 obtained from the tensile test was 76.0 N. This result indicates that the grafted substrate can be reattached.
  • MANa sodium methacrylate
  • both silicon substrates were not peeled by hanging a 100 g weight on one end of the composite, pinching the other end with a clip, and hanging it vertically in the atmosphere.
  • the composite was immersed in deionized water while a 100 g weight (volume: 13 cm 3 ) was suspended vertically (FIG. 4). Thereafter, both members did not peel off even after being left for about 24 hours.
  • the composite was immersed in a 0.5M aqueous sodium chloride solution while hanging a 100 g weight vertically (FIG. 4). Thereafter, after about 1 hour, it was confirmed that one member was naturally peeled off and dropped.
  • the composite formed by this invention can be peeled also by immersing in the 0.5M salt solution. Further, the peeled substrate was washed with deionized water, and when this substrate was bonded by the procedure of Example 1-6, the two adhered again. At that time, the shearing force per 1 cm 2 of the adhesion area was 24N. This indicates that adhesion and peeling can be reversibly and repeatedly by properly using water and saline.
  • the obtained substrate was washed with water using a Soxhlet extractor, immersed in ethylene glycol for several minutes, then washed again with water and dried.
  • a spectroscopic ellipsometer confirmed that a PSPMK graft layer with a thickness of about 135 nm was formed on the silicon substrate.
  • Example 4-4 BUP-fixed stainless steel substrate (manufactured by SUS304, 10 ⁇ 40 ⁇ 1 mm 3 ), BHE-immobilized silicon substrate (10 ⁇ 40 ⁇ 0.5 mm 3 ), methyl methacrylate (MMA, 48.5 mmol), CuBr ( ⁇ 16 mm glass tube) 0.025 mmol), ( ⁇ )-sparteine (0.0510 mmol), ethyl 2-bromoisobutyrate (0.025 mmol) and anisole (1 mL) were added, and freeze degassing was repeated three times, followed by reaction at 75 ° C. for 4 hours. I let you. The substrate was washed with toluene using a Soxhlet extractor and vacuum dried.
  • the film was a PMMA graft thin film having a thickness of about 30 nm.
  • the obtained stainless steel and silicon substrate were again put in a ⁇ 16 mm glass tube, where CuBr (0.022 mmol), 4,4′-dimethyl-2,2′-bipyridine (0.042 mmol), MTAC (12.2 mmol), Ethyl 2-bromoisobutyrate (0.011 mmol), isopropanol (0.23 mL), 2,2,2,2-trifluoroethanol (4.6 mL) was added and freeze degassed three times, followed by reaction at 60 ° C. for 88 hours. It was.
  • the obtained substrate was washed with water using a Soxhlet extractor and dried, and then a block copolymer graft layer made of PMMA-b-PMTAC having a thickness of about 50 nm was formed by an ellipsometer. confirmed.
  • Example 4-5 The adhesion characteristics between members with graft chains formed were evaluated by a tensile test according to the procedure of Example 1-5.
  • the shear force per 1 cm 2 of the adhesion area was 10.3 N.
  • the PSPMK grafted glass substrate prepared in Example 4-1 and the PMTAC grafted poly (vinylidene fluoride-co-trifluoroethylene) film prepared in Example 4-3 were bonded together, the adhesion per 1 cm 2 of the adhesion area The shear force was 25.1N.
  • a load cell having a specification of 1000 N was used, and the pulling speed in the vertical direction was 1 mm / min.
  • a stainless steel plate (10 ⁇ 25 ⁇ 0.3 mm 3 ) was attached to both ends of the adhesive member, and the sample was fixed to an air chuck of a tensile tester.
  • the shearing force obtained by standardizing the force (N) detected in the load cell to the force per 1 cm 2 from the actual adhesion area was found, it was 151 N in the combination of PSPMK and PMTAC.
  • Example 5-2 The film thickness of the brush before and after peeling used in Example 5-1 was determined with a spectroscopic ellipsometer (MASS-102 manufactured by Fibravo). A white laser (wavelength: 380 to 900 nm) using a xenon arc lamp was used as a light source, and measurement was performed at an incident angle of 70 °. The PMTAC brush showed a slight film thickness reduction from 110 nm to 95 nm. The PSPMK brush remained at 165 nm and no change was observed. In either case, one brush thin film did not disappear from the substrate due to peeling, and no significant change in film thickness occurred, suggesting that peeling by the tensile test occurred at the interface between both brushes.
  • MSS-102 spectroscopic ellipsometer
  • FIG. 5 shows a spectrum obtained by analyzing the surface of the member before and after peeling used in Example 5-1 by X-ray photoelectron spectroscopy (XPS).
  • XPS-APEX manufactured by ULVAC-PHI was used, and an Al—K ⁇ monochrome X-ray was irradiated at 150 W under a condition of 1 ⁇ 10 ⁇ 6 Pa to detect photoelectrons in a 45 ° direction with respect to the substrate.
  • Example 5-4 When 2 ⁇ L of water was dropped on the member peeled in Example 5-1, and the 5 mm portion of the substrate edge was pasted again, both members were bonded again, and the shearing force per 1 cm 2 determined from the tensile test was 77.0 N. there were. Further, when the peeled member was bonded again by the same operation, both members were bonded again. At this time, the shear force per 1 cm 2 was 30.0 N. When peeling and re-adhesion by shearing were repeated, the adhesive strength decreased, but the brush remained on the member, indicating that the grafted substrate can be re-adhered.
  • Example 5-5 A 100 g weight (volume: 13 cm 3 ) was vertically suspended at one end of the composite prepared in Example 5-1 and immersed in deionized water (FIG. 3). Thereafter, both members did not peel off even after being left for about 24 hours.
  • the composite was immersed in a 0.5 M aqueous sodium chloride solution while a 100 g weight was suspended vertically (FIG. 4). Thereafter, after about 1 hour, it was confirmed that one member was naturally peeled off and dropped.
  • Example 5-6 After the member peeled here was washed with deionized water and allowed to dry naturally, 2 ⁇ L of water was dropped and the 5 mm portion of the substrate edge was pasted together. The shearing force per 1 cm 2 obtained from the tensile test was 104N.
  • Example 5-7 The surface of the member peeled in Example 5-6 was observed with an atomic force microscope (AFM) (FIG. 6).
  • AFM atomic force microscope
  • the mean square roughness (RMS) of 10 ⁇ m ⁇ 10 ⁇ m square was 1.6 nm before adhesion and 1.8 nm after peeling in a sodium chloride aqueous solution.
  • the surface of the PSPMK brush was 2.0 nm before bonding and 2.4 nm after peeling, and the surface roughness of any brush surface due to bonding and peeling did not increase extremely.
  • Example 5-8 A 100 g weight (volume: 13 cm 3 ) was vertically suspended at one end of the composite prepared in Example 5-1, and immersed in a 0.5 M aqueous sodium chloride solution (FIG. 4). After about 1 hour, one member was peeled off and dropped, and then the member was washed with deionized water, dried naturally, and pasted so that 2 ⁇ L of water was sandwiched between 5 mm of the substrate edge, and both members were bonded again. After repeating peeling and washing in this sodium chloride aqueous solution and adhesion with deionized water twice, a tensile test was conducted. The shear force per cm 2 was 92 N. This indicates that adhesion and peeling can be reversibly and repeatedly by properly using water and saline.
  • Example 6 A tensile tester (EZ-Graph manufactured by Shimadzu Corp.) was prepared by dropping 2 ⁇ L of water onto the 10 ⁇ 40 mm 2 PMANANa substrate and PMTAC substrate prepared in Example 2 and pasting the 5 mm ends of both substrates according to the method of Example 5-1. ) was used to evaluate the adhesive strength. A load cell having a specification of 1000 N was used, and the pulling speed in the vertical direction was 1 mm / min. When the shearing force obtained by normalizing the force (N) detected in the load cell to the force per 1 cm 2 from the actual adhesion area was found, it was 108 N in the combination of PMANAa and PMTAC.
  • Example 7-1 The SPMK grafted glass substrate prepared in Example 4-1 and the PMTAC grafted silicon substrate prepared in Example 1-2 were adhered to each other by the method of Example 5-1.
  • the shearing force per 1 cm 2 of the adhesion area was 86N.
  • Example 7-2 A PMTAC brush was prepared on a glass substrate as in Example 1-3, and the SPMK grafted silicon substrate prepared in Example 1-1 was bonded to each other by the method of Example 5-1.
  • the shearing force per 1 cm 2 of the adhesion area was 107N.
  • Example 7-3 The SPMK grafted glass substrate prepared in Example 4-1 and the PMTAC brush prepared in Example 7-2 were bonded together by the method of Preparation Example 5-1.
  • the shearing force per 1 cm 2 of the adhesion area was 99N.
  • Example 8-1 (Adhesion between Zwitterion Brushes: Example of Sulfobetaine) BHE-immobilized silicon substrate (10 ⁇ 40 ⁇ 0.5 mm 3 ), CuBr (0.025 mmol), 2, ⁇ 16 mm glass tube 2′-bipyridil (0.050 mmol), 3- (N-2-methacryloyloxyethyl-N, N-dimethyl) ammonium propanesulfonate (MAPS, 5.9 mmol), methanol (2.0 mL), water (2. 0 mL) was sequentially added, freeze degassed, and reacted at 30 ° C. for 6 hours. The obtained substrate was washed with TFE using a Soxhlet extractor and dried. An ellipsometer confirmed that the thickness of the PMAPS graft chain was about 100 nm.
  • Example 8-2 The adhesion characteristics between members on which PMAPS graft chains were formed were evaluated by a tensile test.
  • a weight of 500 g (4.9 N) was placed on this, and left standing in hot water for 1.5 hours. Then, the water was removed, and the mixture was allowed to stand in the air at room temperature for 2 hours.
  • a load cell having a 1 kN specification was attached to a tensile tester (EZ-Graph manufactured by Shimadzu Corporation), and the adhesive strength was evaluated at a pulling speed of 1 mm / min.
  • Example 8-2 On the other hand, 2 ⁇ L of water is dropped on the PMAPS substrate at room temperature (25 ° C.) in the atmosphere, the 5 mm portion of the substrate is bonded to each other, and a 500 g (4.9 N) weight is placed on the PMAPS substrate. The PMAPS substrates were bonded together. However, the shear adhesive force obtained from the tensile test was 0.5 N when converted per 1 cm 2 .
  • Example 9-1 (About heat resistance) 2 ⁇ L of water was dropped on the PSPMK brush substrate obtained in Example 1-1, and the end of the PMTAC brush substrate obtained in Example 1-2 was adhered to a 5 mm portion, and a 500 g weight was placed on it for 2 hours at room temperature. Both substrates were bonded by allowing to stand. This was suspended in a constant temperature oven, and a 100 g weight was suspended vertically. Even after 6 hours at 150 ° C., the weight was held without peeling off the adhesive surface.
  • Example 1 A PMTAC graft chain was formed on a silicon substrate in the same manner as in Example 1-2. It was confirmed by an ellipsometer that the film thickness was about 60 nm.
  • Example 4 A PMTAC graft chain was formed on a silicon substrate in the same manner as in Example 1-2. It was confirmed by an ellipsometer that the film thickness was about 60 nm.

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Abstract

La présente invention concerne un procédé d'adhésion pour fixer fermement un élément et une couche d'adhésion, une couche d'adhésion ultra-mince dans lequel l'adhésion et le retrait peuvent être effectués de façon répétée sans laisser de résidus de couche d'adhésion ou résidu d'adhésif et sans endommager un objet à coller lors du retrait de l'objet à coller, et un composite comprenant la couche d'adhésion. Dans le procédé d'adhésion, un premier élément dans lequel une chaîne greffée comprenant un polycation ou un ion dipolaire a été formé sur la surface de celui-ci et un deuxième élément dans lequel une chaîne greffée comprenant un polyanion ou un ion dipolaire a été formé sur la surface de celui-ci sont collées avec lesdites chaînes greffées se faisant mutuellement face.
PCT/JP2010/071891 2009-12-08 2010-12-07 Procédé d'adhésion d'élément et composite polymère WO2011071036A1 (fr)

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JP2016132747A (ja) * 2015-01-21 2016-07-25 三菱電機株式会社 導電性熱剥離固定材、導電性熱剥離固定材を用いた部品の加工方法、及び導電性熱剥離固定材を用いた部品の加工方法に使用されるワイヤ放電加工機

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JP2014099605A (ja) * 2012-11-13 2014-05-29 Samsung Electro-Mechanics Co Ltd 薄膜型チップ素子及びその製造方法
JP2014231543A (ja) * 2013-05-28 2014-12-11 住友ゴム工業株式会社 接着方法及び表面改質弾性体
JP2016132747A (ja) * 2015-01-21 2016-07-25 三菱電機株式会社 導電性熱剥離固定材、導電性熱剥離固定材を用いた部品の加工方法、及び導電性熱剥離固定材を用いた部品の加工方法に使用されるワイヤ放電加工機

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