WO2017119412A1 - 光可逆接着剤 - Google Patents
光可逆接着剤 Download PDFInfo
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- WO2017119412A1 WO2017119412A1 PCT/JP2017/000020 JP2017000020W WO2017119412A1 WO 2017119412 A1 WO2017119412 A1 WO 2017119412A1 JP 2017000020 W JP2017000020 W JP 2017000020W WO 2017119412 A1 WO2017119412 A1 WO 2017119412A1
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- light
- photoresponsive
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- 0 CC(C)(C(O*)=O)N Chemical compound CC(C)(C(O*)=O)N 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- 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
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/10—Removing layers, or parts of layers, mechanically or chemically
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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
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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- 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
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/387—Block-copolymers
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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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
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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
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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- 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
- C09J107/00—Adhesives based on natural rubber
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- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
- C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
Definitions
- the present invention relates to a photoresponsive adhesive having improved response speed and film formability and capable of reversibly repeating adhesion and desorption with light.
- FIG. 1 is a photograph showing the state of fluidization-non-fluidization of a compound by this method. As shown in FIG.
- An object of the present invention is to provide a photoresponsive adhesive that improves such drawbacks of conventional photoresponsive compounds, has high fluidization sensitivity by light irradiation, and can be easily detached. .
- the present inventors have found that a part composed of a polymer liquid crystalline compound containing a photoresponsive group as a part exhibiting a photo phase transition, a light transmissive, and a light responsiveness.
- a photoresponsive adhesive preferably a photoresponsive adhesive
- A is a polymer block of a monomer represented by the following formula (2) having a molecular weight of 1000 to 100000
- B is a molecular weight of 1000 to 400000
- B alone has a wavelength range of 350 to 600 nm. It is a polymer block that does not absorb light, has a glass transition point and a melting point of 20 ° C. or lower, and is liquid or plastically deformable at room temperature.
- R 1 represents the following formula (3) Wherein n is an integer of 2 to 18, m is an integer of 0 to 16, and R 2 is hydrogen or a methyl group)
- the photoresponsive adhesive agent according to [1] which can be desorbed by irradiating light and fluidizing.
- the response sensitivity to light when debonding the adhesive after bonding can be increased.
- the photoresponsive adhesive of the present invention is mainly composed of a polymer compound containing azobenzene having a weight average molecular weight of 3000 to 800,000 and represented by the following general formula (1).
- the adherend can be reversibly adhered and desorbed by fluidizing and non-fluidizing.
- A is a polymerization block of a monomer represented by the following formula (2) having a molecular weight of 1000-100000, B is a molecular weight of 1000-400000, and B alone is light in a wavelength range of 350-600 nm. It is a polymer block that has no absorption, has a glass transition point and a melting point of 20 ° C. or less, and is liquid or plastically deformable at room temperature.
- R 1 represents the following formula (3) (Wherein n is an integer of 2 to 18, m is an integer of 0 to 16, and R 2 is hydrogen or a methyl group)
- the photoresponsive adhesive of the present invention (preferably a photoresponsive adhesive) is solid at room temperature and takes a non-fluid state at the time of bonding, but is fluidized by irradiation with light of a specific wavelength. The adhesive strength is lost, and the adhesive strength is recovered by irradiating the fluidized adhesive with light of another wavelength.
- the adhesive of the present invention has a light-transmitting property together with a polymer liquid crystalline block A containing a photoresponsive group in which the polymer compound of the general formula (1) as a main component exhibits a phase transition by light irradiation.
- a polymer liquid crystalline block A containing a photoresponsive group in which the polymer compound of the general formula (1) as a main component exhibits a phase transition by light irradiation By having the block B having no photoresponsiveness, unlike the conventional light control adhesive, it becomes easy for light to enter deeply into the adhesive layer through the light transmissive block B, and the photoresponsive reaction is performed. Get early.
- the light-transmitting block B is a flexible unit, the photoresponsive adhesive of the present invention is excellent in toughness as a whole and is easily formed into a film.
- the photoresponsive adhesive of the present invention (preferably a photoresponsive adhesive) can be reversibly controlled by light irradiation with different wavelengths, and has a general formula (1
- the unit constituting the block A of the polymer compound has a photoisomerizable azobenzene structure in the side chain and is in a photoisomerizable state even when it loses fluidity, and loses fluidity.
- the photoisomerization reaction in the state softens due to a large change in the molecular structure and transitions to a fluid state, and the reverse reaction occurs by changing the wavelength and irradiating light again or simply leaving it alone. Loss liquidity again.
- the photoresponsive adhesive of the present invention can be performed by repeating such operations.
- the polymer compound having a photoresponsive group of the present invention is a solid under ordinary light at a temperature near room temperature, when used as an adhesive, it is liquefied by irradiation with ultraviolet light and sandwiched between adhesive layers. In addition to this, it is solidified by irradiation with visible light. In addition to this, it can be melted by heating and sandwiched between adhesive layers, and then cooled and hardened for adhesion. Furthermore, after processing into a sheet or tape in advance and sandwiching it between two adhesives, it is liquefied and solidified by the above method and then applied to one side of the adhesive by dissolving it in a solvent, etc. Then, it can be dried and then liquefied and solidified for adhesion.
- the adhesive is a liquid as described above, but even a rubber-like body that is plastically deformed can be similarly bonded.
- the adherend is brought into close contact, and the adhesive is cured. It may be adhered.
- the pressing pressure There is no restriction on the pressing pressure at this time, but it is appropriate if it can be pressed with a finger (0.01-1.00 MPa).
- the thickness of the adhesive layer is several microns, and in the case of ultraviolet light irradiation with an intensity of 20-40 mW / cm 2 , It takes 3 minutes to actually liquefy.
- the following 3 to 5 block copolymer structure in which a colorless flexible portion and a unit causing a phase change by causing a photo phase transition are separated and chemically bonded to each other is obtained.
- the polymer compound of the above formula (1) functions as an adhesive including the properties of rubber because the photo-phase transition unit A showing solid at room temperature serves as an intermolecular crosslinking point at room temperature. Moreover, since only this part undergoes a light phase transition reaction by ultraviolet light irradiation, the whole is liquefied, so that even if the film thickness is increased, a light response can be made with high sensitivity.
- the average molecular weight also has a suitable value, and the weight average molecular weight in terms of standard polystyrene is preferably 3000 to 800,000.
- the photoresponsive adhesive of the present invention selects and irradiates light having a wavelength suitable for the polymer compound of the general formula (1) which is the main component of the adhesive.
- a photoresponsive adhesive selects and irradiates light having a wavelength suitable for the polymer compound of the general formula (1) which is the main component of the adhesive.
- the azobenzene structure present in the side chain of the unit constituting the block A is photoisomerized according to the irradiated light.
- the azobenzene structure is a trans isomer, the fluidity is lost, and when the azobenzene structure is a cis isomer, the fluidity is imparted.
- the adhesive of the present invention it is necessary to isomerize azobenzene from the trans structure to the cis structure.
- light having a wavelength without absorption of the cis isomer is irradiated.
- the adhesive of the present invention can be detached by light irradiation.
- isomerization from the cis configuration to the trans configuration is performed by irradiation with light of 420 to 600 nm, and more preferably with visible light in the vicinity of 500 nm.
- the optimum wavelength of light irradiated to the photoresponsive adhesive varies depending on the molecular structure around the azobenzene structure.
- the material used in this example is preferably 360 to 380 nm.
- the material can be quickly returned to the trans structure by using light of around 500 nm where the absorption of the trans form of azobenzene is weak.
- the adherend bonded by the photoresponsive adhesive of the present invention does not need to be colorless, but a part of ultraviolet light and visible light in the above wavelength range are transmitted from at least one side to the bonding surface. You need to choose one.
- the other may not be light transmissive.
- the adhesive When adhering the adherend and the adhesive before curing, it is desirable that the adhesive is a liquid, but as described above, even a rubber-like body that undergoes plastic deformation can be fluidized by applying a slight stress. After being allowed to stick, it can be cured and bonded. There is no limitation on the pressing pressure at this time, but it is appropriate if it can be pressed with a finger (0.01 to 1.00 MPa).
- the photoreactive block A of the polymer compound of the general formula (1) which is the main component of the adhesive of the present invention, has a polymer structure composed of a monomer having an azobenzene structure in the side chain.
- azobenzene has a trans structure
- the glass transition point and melting point as a homopolymer of the polymer structure are room temperature (25 ° C.) or higher, preferably 40 ° C. or higher.
- the transparent and flexible block B of the polymer compound of the general formula (1) which is the main component of the adhesive of the present invention, must be in a liquid or plastically deformable rubber state at room temperature (25 ° C.). For this reason, the glass transition and melting point are preferably 10 ° C. or lower. Since the role is to lower the pigment concentration of the adhesive, it is of course not dependent on the structure of the polymer, and any liquid polymer that is colorless and does not absorb light or can be plastically deformed may be used.
- colorless as used herein means that the photoreaction of the dye is not inhibited, and therefore means that there is no absorption or little absorption in the wavelength range of 350 to 600 nm.
- the block B is practically limited to several structures.
- Anion polymerization, cation polymerization, and living radical polymerization are known as block copolymer synthesis methods.
- a simple synthesis method includes living radical methods such as ATRP method and RAFT method. According to these synthesis methods, the monomer is vinyl.
- acrylic monomer polymers which are liquid at room temperature.
- a polymer composed of a monomer represented by the following chemical formula (4) corresponds to this.
- styrene-based polymers having a low Tg for example, those of the chemical formula (5) are known.
- R 3 is —C 1 H 2l + 1 , —C 1 H 2l —Si (OSi (CH 3 ) 3 ) 3 , or —C 1 H 2l OH, and R 4 is a hydrogen or methyl group
- l represents an integer of 1 to 18 when R 4 is hydrogen and 4 to 18 when R 4 is a methyl group.
- m represents an integer of 4 to 18.
- the actual block structure was synthesized by using the ATRP (Atom Transfer Radical Polymerization) method (Matyjaszewski, K., Macromolecules 2012, 45, 4015-4039; omitted for many others) as an initiator.
- ATRP Atom Transfer Radical Polymerization
- the polymer obtained by the above polymerization (formula (9): polymerization example of bifunctional initiator and 2-ethylhexyl acrylate) is isolated and described as formula (2) under a copper catalyst again as a polymer initiator.
- the azobenzene-containing monomer is polymerized.
- the polymerization may be continued by adding the monomer of the formula (2) as it is without isolation at the stage where almost all the monomer has been consumed in the first stage.
- the target block copolymer can be obtained by these operations (formula (10): polymerization example of 10- [4- (4-hexylphenylazo) phenoxy] decyl acrylate).
- the present invention uses the above-mentioned photoresponsive adhesive (preferably photoresponsive adhesive), and irradiates light of different wavelengths, so that desorption / adhesion is achieved by reversible fluidization / non-fluidization.
- the method of performing is also included.
- it is preferable to flow by irradiating light in particular, using ultraviolet light having a wavelength of 350 to 390 nm and irradiating with an exposure amount of 0.05 to 10 J / cm 2. Desorption is carried out by converting.
- non-fluidization is performed by using light having a wavelength of 420 to 600 nm, by irradiating light having a wavelength different from that used for fluidization to make it non-fluidized. By doing so, adhesion is performed.
- repeated adhesion / desorption is possible by reversibly fluidizing / non-fluidizing by irradiating light of different wavelengths.
- ConvNMR Monomer conversion rate estimated from NMR MwNMR: Molecular weight of polymer calculated from Conv.NMR EHA: 2-ethylhexyl acrylate (compound of formula (4), R 3
- Example 1 Synthesis of ABA type triblock polymer [poly (6Az10Ac) -b-poly (4SPA) -b-poly (6Az10Ac)] (1a) Synthesis of Poly (4SPA) -1 Then, 25 mg (0.069 mmol) of EBBiB, 9.6 mg (0.069 mmol) of CuBr, 54.6 mg (0.138 mmol) of bpy9, and 4.2 mg (0.069 mmol) of Cu were added.
- Example 2 Synthesis of ABA-type triblock polymer [poly (6Az10Ac) -b-poly (EHA) -b-poly (6Az10Ac)] (1a) Synthesis of Poly (EHA) -1 Then, 11.6 mg (0.032 mmol) of EBBiB, 4.6 mg (0.032 mmol) of CuBr, 26.1 mg (0.064 mmol) of bpy9, and 2.0 mg (0.032 mmol) of Cu were added.
- Poly [(6Az10Ac) -b- (4SPA) -b- (6Az10Ac)]-1 is placed on a slide glass substrate (Matsunami white cut No. 1) using an LED light source (Hamamatsu Photonics LC-L1V3) Then, ultraviolet rays having a center wavelength of 365 nm (half-value width 13 nm) were irradiated at room temperature (about 25 ° C.). When irradiated for 0.5 minutes (3 J / cm 2 ), the powder changed into a syrupy viscous liquid. This corresponds to twice the speed of liquefaction of a conventional sugar alcohol ester material (Patent Document 2).
- Example 4 Liquefaction test of Poly [(6Az10Ac) -b- (4SPA) -b- (6Az10Ac)]-1 by ultraviolet irradiation (2) Take approximately 1 mg of Poly [(6Az10Ac) -b- (4SPA) -b- (6Az10Ac)]-1 that has not been irradiated with light, and sandwich it in a melted state on two glass substrates while heating to an area of 15 mm x 15 mm Spread out. The glass substrate was adhere
- Example 6 Liquefaction and adhesion test for other triblock polymers of the present invention Other than Poly [(6Az10Ac) -b- (4SPA) -b- (6Az10Ac)]-1 obtained in Examples 1 and 2 Triblock polymer [poly (6Az10Ac) -b-poly (4SPA) -b-poly (6Az10Ac)]-2-4, [poly (6Az10Ac) -b-poly (EHA) -b-poly (6Az10Ac)]- For 1-2, the same results as in Examples 3-5 were obtained.
- AB type diblock polymer Synthesis of EBiB-PEHA-b-P6Az10Ac-Br (a) Polymerization of EBiB-PEHA-Br A stir bar was placed in a pressure tube and 4.0 ul of Ethyl 2-bromoisobutyrate (EBiB) was added. (0.027 mmol), CuBr2 1.8 mg (0.0081 mmol), Me6TREN 2.2 ul (0.0081 mmol), and ascorbic acid 29 mg (0.16 mmol) were added.
- EBiB Ethyl 2-bromoisobutyrate
- Example 7 Fusion adhesion of the triblock polymer of the present invention and the diblock polymer of Comparative Example 1, liquefaction by ultraviolet light irradiation, and adhesion test by visible light irradiation
- Two 1.5 cm x 5 cm x 3 mm glass substrates A sample with a polymer width (over 10cm) melted, sandwiched between them, and returned to room temperature for adhesion, and a sample irradiated with 365nm ultraviolet light (Hamamatsu Photonics LC-L1V3) for 2-3 minutes
- a sample that was irradiated with visible light of 510 nm (Luxeon cyan 5w LXHL-LE5C) for 10 to 15 minutes was subjected to a tensile test with 5 samples to determine the tensile shear bond strength. It was set as the adhesive strength (FIG. 2).
- the summarized results are shown in Table 1.
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Abstract
Description
[2] 光を照射して流動化することにより脱着を行うことが可能な[1]に記載の光応答性粘接着剤。
[3] 波長350~390nmの紫外光を用い、その露光量を0.05~10J/cm2として照射して流動化することにより脱着を行うことを特徴とする[2]に記載の光応答性粘接着剤。
[4] 流動化に用いる光とは異なる波長の光を照射して非流動化することにより接着を行うことが可能な[1]~[3]のいずれかに記載の光応答性粘接着剤。
[5] 波長420~600nmの光を用いて非流動化することを特徴とする[4]に記載の光応答性粘接着剤。
[6] 異なる波長の光を照射して可逆的に流動化・非流動化させることにより繰り返しの接着脱着が可能な[1]~[5]のいずれかに記載の光応答性粘接着剤。
EBBiB:Ethylene bis(2-bromoisobutyrate)(式(6)の化合物)
4SPA:(3-Acryloxypropyl)tris(trimethylsiloxy)silane(式(4)、R3=-C3H6-Si(OSi(CH3)3)3、R4=Hの化合物)
6Az10Ac:10-(4-(4-hexylphenylazo)phenoxy)decyl acrylate(式(2)中、R1の式(3)におけるm=6、n=10、R2=Hの化合物)
Bpy6:4,4'-dinonyl-2,2'-bipyridyl(以下に示す式(11)の化合物)
ConvNMR:NMRから見積もったモノマー転換率
MwNMR:Conv.NMRから計算したポリマーの分子量
EHA:2-ethylhexyl acrylate(式(4)、R3=-3-C8H17(すなわちl=2)、R4=Hの化合物)
Me6TREN:tris[2-(dimethylamino)ethyl]amine(以下に示す式(12)の化合物)
(1a)Poly(4SPA)-1の合成
耐圧管に撹拌子を入れ、EBBiBを25mg(0.069mmol)、CuBrを9.6mg(0.069mmol)、bpy9を54.6mg(0.138mmol)、Cuを4.2mg(0.069mmol)加えた。窒素雰囲気にした無菌パックの中でこれにテトラヒドロフラン(THF)を0.67ml加えて、全体が均一な溶液になるまで撹拌し、その後4SPAを0.62ml(1.38mmol)加えて密閉し、55℃のオイルバスで6時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し、CuBr2を加えて軽く混ぜた後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は413mg、ConvNMR=93%、MwNMR=7588gmol-1であった。
耐圧管に撹拌子を入れ、Poly(4SPA)-1を250mg(0.033mmol)、CuBrを19mg(0.13mmol)、bpy9を108mg(0.26mmol)、Cuを16.8mg(0.26mmol)、6Az10Acを305mg(0.66mmol)加えた。Ar雰囲気にした無菌パックの中でこれにTHFを0.66ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、シリカカラムで精製した。収量は250mg、ConvNMR=68%、MwNMR=13880gmol-1であった。
耐圧管に撹拌子を入れ、EBBiBを18mg(0.05mmol)、CuBrを7.2mg(0.05mmol)、bpy9を41mg(0.10mmol)、Cuを3.2mg(0.05mmol)加えた。窒素雰囲気にした無菌パックの中でこれにTHFを0.3ml加えて、全体が均一な溶液になるまで撹拌し、その後4SPAを0.28ml(0.61mmol)加えて密閉し、55℃のオイルバスで6時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し、CuBr2を加えて軽く混ぜた後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は64mg、ConvNMR=100%、MwNMR=4896gmol-1であった。
耐圧管に撹拌子を入れ、Poly(4SPA)-2を64mg(0.013mmol)、CuBrを7.5mg(0.052mmol)、bpy9を43mg(0.10mmol)、Cuを6.7mg(0.10mmol)、6Az10Acを121mg(0.26mmol)加えた。そこにAr雰囲気にした無菌パックの中でTHFを0.26ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、シリカカラムで精製した。収量は32mg、ConvNMR=60%、MwNMR=10448gmol-1であった。
耐圧管に撹拌子を入れ、EBBiBを6.3mg(0.017mmol)、CuBrを2.4mg(0.017mmol)、bpy9を14mg(0.034mmol)、Cuを1.1mg(0.017mmol)加えた。窒素雰囲気にした無菌パックの中でこれにTHFを0.3ml加えて、全体が均一な溶液になるまで撹拌し、その後4SPAを0.28ml(0.61mmol)加えて密閉し、55℃のオイルバスで6時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し、CuBr2を加えて軽く混ぜた後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は111mg、ConvNMR=100%、MwNMR=14280gmol-1であった。
耐圧管に撹拌子を入れ、Poly(4SPA)-3を111mg(0.0078mmol)、CuBrを7.5mg(0.031mmol)、bpy9を25mg(0.062mmol)、Cuを4.0mg(0.062mmol)、6Az10Acを72mg(0.15mmol)加えた。Ar雰囲気にした無菌パックの中でこれにTHFを0.15ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、シリカカラムで精製した。収量は43mg、ConvNMR=86%、MwNMR=22237gmol-1であった。
耐圧管に撹拌子を入れ、EBBiBを4.9mg(0.013mmol)、CuBrを1.9mg(0.013mmol)、bpy9を11mg(0.026mmol)、Cuを0.83mg(0.013mmol)加えた。窒素雰囲気にした無菌パックの中でこれにTHFを0.3ml加えて、全体が均一な溶液になるまで撹拌し、その後4SPAを0.28ml(0.61mmol)加えて密閉し、55℃のオイルバスで6時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し、CuBr2を加えて軽く混ぜた後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は154mg、ConvNMR=100%、MwNMR=18360gmol-1であった。
耐圧管に撹拌子を入れ、Poly(4SPA)-4を154mg(0.0084mmol)、CuBrを4.8mg(0.034mmol)、bpy9を27mg(0.068mmol)、Cuを4.3mg(0.068mmol)、6Az10Acを77mg(0.17mmol)加えた。Ar雰囲気にした無菌パックの中でこれにTHFを0.17ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、シリカカラムで精製した。収量は37mg、ConvNMR=56%、MwNMR=23541gmol-1であった。
(1a)Poly(EHA)-1の合成
耐圧管に撹拌子を入れ、EBBiBを11.6mg(0.032mmol)、CuBrを4.6mg(0.032mmol)、bpy9を26.1mg(0.064mmol)、Cuを2.0mg(0.032mmol)加えた。窒素雰囲気にした無菌パックの中でこれにTHFを0.67ml加えて、全体が均一な溶液になるまで撹拌し、その後EHAを0.30ml(1.44mmol)加えて密閉し、55℃のオイルバスで8時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し、CuBr2を加えて軽く混ぜた後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は162mg、ConvNMR=71%、MwNMR=5878gmol-1であった。
耐圧管に撹拌子を入れ、poly(EHA)-1を162mg(0.028mmol)、CuBrを15.8mg(0.11mmol)、bpy9を89.8mg(0.22mmol)、Cuを14.0mg(0.22mmol)、6Az10Acを255mg(0.55mmol)加えた。Ar雰囲気にした無菌パックの中でこれにTHFを0.55ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、シリカカラムで精製した。収量は60mg、ConvNMR=68%、MwNMR=12170gmol-1であった。
耐圧管に撹拌子を入れ、EBBiBを5.8mg(0.016mmol)、CuBr2を2.2mg(0.0099mmol)、Me6TRENを2.7ul(0.0099mmol)、アスコルビン酸を16.9mg(0.20mmol)加えた。Ar雰囲気にした無菌パックの中でこれにトルエンを0.29ml加えて、全体が均一な溶液になるまで撹拌し、その後EHAを0.30ml(0.14mmol)加えて密閉し、55℃のオイルバスで4時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却した後、中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は131mg、ConvNMR=94%、MwNMR=15566gmol-1であった。
耐圧管に撹拌子を入れ、Poly(EHA)-2を131mg(0.0084mmol)、CuBr2を1.87mg(0.0084mmol)、Me6TRENを2.4ul(0.0084mmol)、アスコルビン酸を14.8mg(0.084mmol)、6Az10Acを136mg(0.29mmol)加えた。Ar雰囲気にした無菌パックの中でこれにトルエンを0.20ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、中性アルミナ粉のカラムに通した後、メタノール:アセトン=1:2の混合溶媒で再沈殿、遠心分離によって精製した。収量は100mg、ConvNMR=47%、MwNMR=23166gmol-1であった。
Poly[(6Az10Ac)-b-(4SPA)-b-(6Az10Ac)]-1を極微量、スライドガラス基板(松波白切放 No.1)上にとり、LED光源(浜松フォトニクスLC-L1V3)を用いて、中心波長365nm(半値幅13nm)の紫外線を室温(約25℃)下で照射した。0.5分間(3J/cm2)照射したところ、粉末は水飴状の粘性液体に変化した。これは、従来の糖アルコールエステル材料(特許文献2)の液化の2倍の速さに相当する。
光未照射のPoly[(6Az10Ac)-b-(4SPA)-b-(6Az10Ac)]-1を約1mgとり、加熱しながら、2枚のガラス基板に融解した状態で挟み込み、面積15mm×15mmに広げた。これを冷却することで、ガラス基板が接着された。これにLED光源(浜松浜松フォトニクスLC-L1V3)を用いて、中心波長365nmの紫外線を室温(約25℃)下で0.5分間照射(3J/cm2)し、液化したところ、ガラス2枚を指でずらすことができた。
紫外光照射により液化したサンプルを挟んだ上記ガラス基板2枚にLED光源(Luxeon cyan 5w LXHL-LE5C)を用いて中心波長510nmの可視光を3分間照射(6J/cm2)したところ、接着面は透明なままだったが、基板2枚を指でずらそうとしてもずれなかった。このガラス基板2枚をそれぞれ逆方向にひっぱったところ、剥離することはなかった。
実施例1及び2で得られた、Poly[(6Az10Ac)-b-(4SPA)-b-(6Az10Ac)]-1 以外のトリブロックポリマー[poly(6Az10Ac)-b-poly(4SPA)-b-poly(6Az10Ac)]-2~4、[poly(6Az10Ac)-b-poly(EHA)-b-poly(6Az10Ac)]-1~2についても、実施例3~5と同様の結果が得られた。
(a)EBiB-PEHA-Brの重合
耐圧管に撹拌子を入れ、Ethyl 2-bromoisobutyrate(EBiB)を4.0ul(0.027mmol)、CuBr2を1.8mg(0.0081mmol)、Me6TRENを2.2ul(0.0081mmol)、アスコルビン酸を29mg(0.16mmol)加えた。Ar雰囲気にした無菌パックの中でこれにトルエンを0.48ml加えて、全体が均一な溶液になるまで撹拌し、その後EHAを0.50ml(2.4mmol)加え密閉し、55℃のオイルバスで5時間撹拌しながら加熱した。その後冷蔵庫で15分間冷却し中性アルミナ粉のカラムに通した。それをメタノールで再沈殿・遠心分離して精製した。収量は200mg、ConvNMR=96%、MwNMR=15897gmol-1であった。
耐圧管に撹拌子を入れ、EBiB-PEHA-Brを200mg(0.013mmol)、CuBr2を2.8mg(0.013mmol)、Me6TRENを3.5ul(0.013mmol)、アスコルビン酸を22mg(0.13mmol)、6Az10Acを0.12g(2.5mmol)加えた。Ar雰囲気にした無菌パックの中でこれにトルエンを0.17ml加えて、全体が均一な溶液になるまでお湯で加温しながら撹拌して密閉し、55℃のオイルバスで24時間撹拌しながら加熱した。反応後、再沈殿(メタノール:アセトン=1:2)・遠心分離して精製した。収量は130mg、ConvNMR=61%、MwNMR=21541gmol-1であった。
耐圧管に撹拌子を入れ、アゾビスイソブチロニトリルを6.6mg(0.040mmol)、6Az10Acを185mg(0.40mmol)加えた。Ar雰囲気にした無菌パックの中でこれにトルエンを0.50ml加えて、全体が均一な溶液になるまで撹拌し、その後EHAを0.33ml(1.6mmol)加え密閉し、80℃のオイルバスで1時間撹拌しながら加熱した。それをメタノールで再沈殿・遠心分離して液状の高分子180mgを得た。ConvNMR(EHA)=52%、ConvNMR(6Az10Ac)=60%、MwGPC=53790gmol-1、MWD=2.22であった。
1.5cm×5cm×3mmのガラス基板2枚を1.5cm幅重ね合わせ、その間に合成した高分子(10mg弱)を溶融させて挟み込み、室温に戻して接着した試料、これに365nmの紫外光(浜松フォトニクスLC-L1V3)を2~3分照射した試料、および、これにさらに510nmの可視光(Luxeon cyan 5w LXHL-LE5C)を10~15分照射した試料について、サンプル数5本で引っ張り試験を行い、引っ張り剪断接着強度を求め、5本の平均を接着強度とした(図2)。まとめた結果を表1に示す。
Claims (6)
- 光を照射して流動化することにより脱着を行うことが可能な、請求項1に記載の光応答性粘接着剤。
- 波長350~390nmの紫外光を用い、その露光量を0.05~10J/cm2として照射して流動化することにより脱着を行うことを特徴とする、請求項2に記載の光応答性粘接着剤。
- 流動化に用いる光とは異なる波長の光を照射して非流動化することにより接着を行うことが可能な、請求項1~3のいずれか一項に記載の光応答性粘接着剤。
- 波長420~600nmの光を用いて非流動化することを特徴とする、請求項4に記載の光応答性粘接着剤。
- 異なる波長の光を照射して可逆的に流動化・非流動化させることにより繰り返しの接着脱着が可能な、請求項1~5のいずれか一項に記載の光応答性粘接着剤。
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WO2020213641A1 (ja) * | 2019-04-19 | 2020-10-22 | 国立研究開発法人産業技術総合研究所 | 光応答性ポリビニルエーテル化合物および光可逆接着剤 |
JP2020180177A (ja) * | 2019-04-23 | 2020-11-05 | コニカミノルタ株式会社 | 光応答性高分子化合物 |
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JPWO2017119412A1 (ja) | 2018-04-12 |
JP6334072B2 (ja) | 2018-05-30 |
TW201736555A (zh) | 2017-10-16 |
EP3401377A1 (en) | 2018-11-14 |
TWI700348B (zh) | 2020-08-01 |
US10767088B2 (en) | 2020-09-08 |
US20190016933A1 (en) | 2019-01-17 |
EP3401377A4 (en) | 2019-09-11 |
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