WO2017187800A1 - 造形ステージ用粘着シートおよび積層造形装置 - Google Patents
造形ステージ用粘着シートおよび積層造形装置 Download PDFInfo
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- WO2017187800A1 WO2017187800A1 PCT/JP2017/009038 JP2017009038W WO2017187800A1 WO 2017187800 A1 WO2017187800 A1 WO 2017187800A1 JP 2017009038 W JP2017009038 W JP 2017009038W WO 2017187800 A1 WO2017187800 A1 WO 2017187800A1
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- pressure
- sensitive adhesive
- adhesive layer
- adhesive sheet
- modeling stage
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/245—Platforms or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/308—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive tape or sheet losing adhesive strength when being stretched, e.g. stretch adhesive
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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
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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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a technique for fixing and separating a modeling stage included in an additive manufacturing apparatus and a modeled object formed thereon.
- the layered manufacturing apparatus includes a modeling stage on which a three-dimensional model is formed.
- a so-called additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, a powder sintering method, a powder fixing method, a sheet lamination method, or the like is performed. Is formed.
- Such an additive manufacturing apparatus is described in, for example, the following Patent Documents 1 to 4.
- a modeled object in the middle of formation may be fixed on the surface of the modeled stage in the process of forming a modeled object on the modeled stage.
- a tool such as a scraper having a sharp tip is inserted between the modeling stage and the modeling object fixed on the surface to separate the modeling stage and the modeling object.
- the present invention has been conceived under such circumstances, and a modeling object that is formed on the modeling stage of the layered modeling apparatus and can be fixed on the surface of the stage is shaped during modeling.
- Providing a pressure-sensitive adhesive sheet for a modeling stage that is fixed or fixed on the stage and easily removed from the modeling stage after modeling, and suitable for using such a pressure-sensitive adhesive sheet for modeling stage An object is to provide an additive manufacturing apparatus.
- an adhesive sheet for a modeling stage is provided.
- This modeling stage pressure-sensitive adhesive sheet is used by being bonded to the modeling object forming surface of the modeling stage included in the layered modeling apparatus, and at least one of which the adhesive force can be reduced due to the adhesive strength reduction measure
- a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive (a layer capable of lowering adhesive strength)
- the adhesive strength reducing measure is, for example, heating, cooling, electromagnetic wave irradiation, voltage application, liquid supply, stretching or deformation, magnetic field application, or pressure change for the adhesive strength reducing layer.
- the adhesive strength can be reduced according to the adhesive strength reduction measure.
- This modeling stage pressure-sensitive adhesive sheet comprises a single pressure-sensitive adhesive layer, a pressure-sensitive adhesive layer (stage-side pressure-sensitive adhesive layer) for forming a pressure-sensitive adhesive surface to the modeling stage, and at least one other pressure-sensitive adhesive layer and / or Or what has a laminated structure containing a base material may be used, and what is called a double-sided adhesive sheet may be sufficient, and what is called a single-sided adhesive sheet may be sufficient.
- the adhesive force-reducible layer may be a stage-side pressure-sensitive adhesive layer or other pressure-sensitive adhesive in the above laminated structure other than the stage-side pressure-sensitive adhesive layer. It may be an agent layer.
- the pressure sensitive adhesive sheet for modeling stage may take the form of, for example, a wound pressure sensitive adhesive tape.
- the pressure-sensitive adhesive sheet for this modeling stage can be specifically used as follows. First, the pressure-sensitive adhesive sheet for the modeling stage is bonded to the modeling object forming surface of the modeling stage included in the additive manufacturing apparatus for forming the modeling object via the stage-side pressure-sensitive adhesive layer. When the apparatus is in operation, a target model is gradually formed through a predetermined process on a model stage having the pressure-sensitive adhesive sheet on the model-formed surface. In the process of forming a modeled object on the modeling stage, the pressure-sensitive adhesive sheet for the main modeling stage is adhered to the surface of the modeling stage, and the modeled object being formed is fixed on the surface of the main pressure-sensitive adhesive sheet on the modeling stage.
- the modeled object in the middle of formation is in a state of being fixed to the modeling stage via the pressure-sensitive adhesive sheet.
- the adhesive force reduction measure is performed with respect to this adhesive sheet on a modeling stage. Thereby, the adhesive force of the adhesive strength-reducible layer of the pressure-sensitive adhesive sheet for this modeling stage is reduced, and the fixing state of the molded object with respect to the modeling stage via the pressure-sensitive adhesive sheet is released. Thereafter, the modeled object whose fixing state is released from the modeling stage is removed from the modeling stage.
- the molded object is removed from the modeling stage as the pressure-sensitive adhesive sheet for the modeling stage is peeled off at a predetermined interface formed by the pressure-sensitive adhesive layer. It becomes possible.
- the pressure-sensitive adhesive sheet for the modeling stage has an adhesive strength-reducing layer that forms a pressure-sensitive adhesive surface for a molded product in the process of forming a molded product, for example, the adhesive power-reducible layer in which the adhesive strength is reduced due to an adhesive strength reduction measure
- a pressure-sensitive adhesive sheet having a laminated structure of a stage-side pressure-sensitive adhesive layer and a substrate, which has a sufficient adhesive force with respect to a modeling stage and whose adhesive strength cannot be intentionally lowered after formation of a molded article
- the molded object remains on the surface of the pressure-sensitive adhesive sheet.
- the adhesive sheet is unlikely to peel off in the fixed area.
- the modeling stage that it has and the modeled object to be formed are both hard and difficult to bend and deformed.
- the pressure-sensitive adhesive sheet for modeling stage according to the first aspect of the present invention has a pressure-sensitive adhesive layer (adhesive strength-reducible layer) that can reduce the pressure-sensitive adhesive force due to the pressure-reducing measures.
- a pressure-sensitive adhesive layer adheresive strength-reducible layer
- the pressure-sensitive adhesive sheet for the modeling stage according to the first aspect of the present invention is fixed or positioned on the modeling stage during modeling for a modeled object formed on the modeling stage included in the layered modeling apparatus. It is suitable for fixing and making it easy to remove from the modeling stage after modeling. That is, the pressure-sensitive adhesive sheet for a modeling stage is suitable for exhibiting both conflicting characteristics such as good fixing or fixing of a molded object on the modeling stage and ease of removal.
- the requirement for the development of contradictory characteristics such as good fixation or position fixing and ease of removal with respect to the modeling object on the modeling stage is a delicate one that contains many thin structural parts and breaks. Especially strong in cases where it is easy, this pressure-sensitive adhesive sheet for modeling stage is suitable for meeting such requirements.
- a scraper having a sharp tip is used to remove the modeled object from the modeling stage. It is possible to avoid the use of tools. According to the use of the pressure-sensitive adhesive sheet for the modeling stage, even if a tool such as a scraper is temporarily used to remove the modeled object from the modeling stage, the tool is applied to the predetermined interface, for example, in the adhesive force-decreasing layer. Can be inserted with a relatively small force to facilitate separation between the modeling stage and the modeled object. Therefore, the use of the pressure-sensitive adhesive sheet for the modeling stage contributes to avoiding or suppressing damage to the modeled object or the modeling stage when the modeled object is removed from the modeling stage.
- the above-mentioned pressure-sensitive adhesive layer which is a layer capable of reducing the pressure-sensitive adhesive force, is a heat-peelable pressure-sensitive adhesive layer, and the pressure-sensitive adhesive strength reduction measure is heating of the pressure-sensitive adhesive layer.
- the said heat peeling type adhesive layer contains a thermal expansion agent, for example.
- the thermal expansion agent is, for example, a thermally expandable microsphere that includes a component that is gasified by heating and a shell that encloses the component and can expand and / or break by gasification of the component. According to such a configuration, it is possible to appropriately realize the above-described fixing and detachment related to the modeled object on the modeling stage by using the thermal peeling technique related to the pressure-sensitive adhesive layer.
- the above-mentioned pressure-sensitive adhesive layer that is a layer capable of reducing the pressure-sensitive adhesive force is a cooling release type pressure-sensitive adhesive layer, and the pressure-sensitive adhesive force reducing measure is cooling of the pressure-sensitive adhesive layer.
- the said cooling peeling type adhesive layer contains a side chain crystalline polymer, for example. According to such a structure, it is possible to implement
- the above-mentioned pressure-sensitive adhesive layer that is a layer capable of reducing the pressure-sensitive adhesive force is an electromagnetic wave peeling type pressure-sensitive adhesive layer
- the pressure-sensitive adhesive force reduction measure is electromagnetic wave irradiation to the pressure-sensitive adhesive layer.
- the electromagnetic wave peelable pressure-sensitive adhesive layer contains, for example, an electromagnetic wave curable component. According to such a structure, it is possible to implement
- the above-mentioned pressure-sensitive adhesive layer that is a layer capable of reducing the pressure-sensitive adhesive force is an electrodetachable pressure-sensitive adhesive layer
- the pressure-reducing measure is voltage application to the pressure-sensitive adhesive layer.
- the electrodetachable pressure-sensitive adhesive layer contains, for example, an electrolyte. This electrolyte is preferably an ionic liquid.
- the content of the electrolyte in the electrodetachable pressure-sensitive adhesive layer is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. According to such a configuration, it is possible to appropriately realize the above-described fixing and detachment related to the modeled object on the modeling stage by using the electric peeling technique related to the pressure-sensitive adhesive layer.
- the above-mentioned pressure-sensitive adhesive layer which is a pressure-reducible layer is a liquid peelable pressure-sensitive adhesive layer
- the pressure-reducing measure is liquid supply to the pressure-sensitive adhesive layer.
- the liquid peelable pressure-sensitive adhesive layer contains, for example, a water-soluble pressure-sensitive adhesive. According to such a structure, it is possible to implement
- the pressure-sensitive adhesive sheet for modeling stage has a laminated structure including the above-mentioned pressure-sensitive adhesive layer that is a pressure-reducible layer and a stretchable base material, and the pressure-reducing measure is an extension of the pressure-sensitive adhesive sheet for modeling stage. is there.
- the elongation at break (elongation at break), which is measured for the pressure-sensitive adhesive sheet for the present modeling stage, in accordance with the method for measuring “elongation” described in JIS K K7311-1995 is preferably 300% or more. According to such a structure, it is possible to implement
- an additive manufacturing apparatus is provided.
- This additive manufacturing apparatus is an additive manufacturing apparatus capable of using the modeling sheet pressure-sensitive adhesive sheet according to the first aspect of the present invention, and is formed on the modeling stage and the modeling stage adhesive sheet.
- an adhesive strength reducing means for performing an adhesive strength reducing measure for the adhesive layer.
- Such an additive manufacturing apparatus is suitable for using the above-described pressure-sensitive adhesive sheet for modeling stage according to the first aspect of the present invention.
- the pressure-sensitive adhesive layer as the pressure-reducible layer of the pressure-sensitive adhesive sheet for modeling stage is an electromagnetic wave peeling type pressure-sensitive adhesive layer, It is an electromagnetic wave irradiation means for performing electromagnetic wave irradiation.
- the electromagnetic wave peelable pressure-sensitive adhesive layer contains, for example, an electromagnetic wave curable component.
- the pressure-sensitive adhesive layer as a layer capable of reducing the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet for modeling stage is an electrodetachable pressure-sensitive adhesive layer
- the pressure-sensitive adhesive strength reducing means is It is a voltage application means for performing voltage application.
- the electrodetachable pressure-sensitive adhesive layer contains, for example, an electrolyte. This electrolyte is preferably an ionic liquid.
- the content of the electrolyte in the electrodetachable pressure-sensitive adhesive layer is preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive. According to the layered manufacturing apparatus having such a configuration, it is possible to appropriately realize the above-described fixing and detachment related to the modeled object on the modeling stage by using the electric peeling technique related to the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive in the pressure-reducible layer preferably contains an acrylic pressure-sensitive adhesive, and the thickness of the pressure-sensitive adhesive layer is preferably 1 to 1000 nm.
- FIG. 1 It is a fragmentary sectional view of the pressure sensitive adhesive sheet for modeling stages concerning one embodiment of the present invention. It is a figure showing the usage condition of the adhesive sheet for modeling stages which concerns on this invention.
- FIG. 1 The modification of the adhesive sheet for modeling stages shown in FIG. 1 is represented.
- FIG. 4 The modification of the adhesive sheet for modeling stages shown in FIG. 4 is represented.
- FIG. 4 It is a fragmentary sectional view of the pressure sensitive adhesive sheet for modeling stages concerning one embodiment of the present invention.
- FIG. 6 is represented. It is a fragmentary sectional view of the pressure sensitive adhesive sheet for modeling stages concerning one embodiment of the present invention.
- the modification of the adhesive sheet for modeling stages shown in FIG. 8 is represented. It is a fragmentary sectional view of the pressure sensitive adhesive sheet for modeling stages concerning one embodiment of the present invention.
- the modification of the adhesive sheet for modeling stages shown in FIG. 10 is represented. It is a fragmentary sectional view of the pressure sensitive adhesive sheet for modeling stages concerning one embodiment of the present invention.
- the modification of the adhesive sheet for modeling stages shown in FIG. 12 is represented.
- 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention. 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention.
- 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention.
- 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention.
- 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention.
- 1 is a partial configuration diagram of an additive manufacturing apparatus according to an embodiment of the present invention.
- It is a perspective view of the molded article produced for the peeling force measurement which concerns on each adhesive sheet of Examples 6 and 7 and Comparative Example 1.
- FIG. 1 is a perspective view of the molded article produced for the peeling force measurement which concerns on each adhesive sheet of Examples 6 and 7 and Comparative Example 1.
- FIG. 1 is a partial cross-sectional view of a pressure-sensitive adhesive sheet X1 that is a pressure-sensitive adhesive sheet for a modeling stage according to an embodiment of the present invention.
- the pressure-sensitive adhesive sheet X1 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the substrate S1 and the pressure-sensitive adhesive layers 11 and 12.
- the base material S1 of the adhesive sheet X1 is a part for functioning as a support in the adhesive sheet X1.
- Examples of the material for forming such a base material S1 include paper materials, nonwoven fabrics, and plastic films.
- Examples of the paper material for forming the substrate S1 include Japanese paper, crepe paper, craft paper, glassine paper, and synthetic paper.
- Examples of the nonwoven fabric material for forming the substrate S1 include pulp such as hemp pulp and wood pulp, rayon, acetate fiber, polyester fiber, polyamide fiber, polyolefin fiber, and polyvinyl alcohol fiber. In order to bond the nonwoven fabric fibers, for example, a binder resin is impregnated into the fiber body.
- Examples of the plastic film for forming the substrate S1 include a polyolefin film, a polyester film, a polyurethane film, a polyimide resin film, a polyamide resin film, a soft vinyl chloride resin film, and a vinyl acetate resin film.
- Examples of the polyolefin film include a polyethylene film, a polypropylene film, and a film made of an ethylene-propylene copolymer.
- Examples of the polyester film include a polyethylene terephthalate film.
- the base material S1 of the pressure-sensitive adhesive sheet X1 may be made of one type of material, or may be made of two or more types of materials.
- the base material S1 may be a laminate including a plurality of layers having different constituent materials.
- the surface treatment for the adhesive improvement with the adjacent adhesive layer may be given to the adhesive layer 11 side surface and / or the adhesive layer 12 side surface in base material S1.
- Examples of such surface treatment include physical treatment such as corona treatment and plasma treatment, and chemical treatment such as undercoating treatment.
- the thickness is, for example, 10 to 300 ⁇ m.
- the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet X1 is a heat-peeling pressure-sensitive adhesive layer (adhesive strength-reducible layer) whose adhesive strength can be reduced by heating (adhesive strength reduction measure), and has an adhesive surface 11a.
- the pressure-sensitive adhesive layer 11 which is such a heat-peelable pressure-sensitive adhesive layer is made of a pressure-sensitive adhesive composition whose adhesive strength is significantly reduced by heating from room temperature, for example.
- an adhesive and a thermal expansion agent are contained.
- the thermal expansion agent is a fine particle that can be expanded and / or foamed by heating.
- the pressure-sensitive adhesive layer 11 containing such a thermal expansion agent expands when heated to expand and foam the thermal expansion agent.
- an uneven shape is generated on the surface including the adhesive surface 11a.
- the pressure-sensitive adhesive layer 11 is subjected to such heating in a state where the pressure-sensitive adhesive surface 11a is adhered to the adherend, an uneven shape is generated on the pressure-sensitive adhesive surface 11a of the pressure-sensitive adhesive layer 11 which expands, and adhesion to the adherend.
- the adhesion area of the adhesive layer 11 or the adhesive surface 11a is reduced, and the adhesive force of the adhesive layer 11 to the adherend is reduced.
- Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 11 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide. Type adhesives and urethane type adhesives. From the viewpoint of good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 11, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 11.
- An acrylic pressure-sensitive adhesive or acrylic polymer is a polymer containing monomer units derived from an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester as the main monomer unit having the largest mass ratio.
- the acrylic polymer is derived from, for example, a (meth) acrylic acid alkyl ester having an alkyl group having 22 or less carbon atoms as a main monomer unit. Includes units.
- the main monomer unit is a monomer unit occupying the largest mass ratio in the acrylic polymer.
- (Meth) acryl means “acryl” and / or “methacryl”.
- alkyl group having 22 or less carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, isodecyl group, dodecyl group, lauryl group, Examples include tridecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and docosyl groups.
- the acrylic polymer contained in the pressure-sensitive adhesive layer 11 one type of (meth) acrylic acid alkyl ester may be used, or two or more types of (meth) acrylic acid alkyl ester may be used. Also good.
- the acrylic polymer is a (meth) acrylic acid alkyl ester from the viewpoint of modifying the cohesive force, heat resistance, and the like in the pressure-sensitive adhesive layer 11. It may also contain monomer units derived from other types of monomers that are polymerized together. Examples of such copolymerizable monomers include carboxy group-containing monomers, hydroxyl group-containing monomers, sulfonic acid group-containing monomers, amide monomers, (meth) acrylate alkylamino monomers, maleimide monomers, vinyl monomers, cyano monomers. Examples include acrylate monomers, epoxy group-containing acrylic monomers, and polyfunctional monomers.
- Examples of the carboxy group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
- Examples of the hydroxyl group-containing monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, (meth ) Hydroxydecyl acrylate, hydroxy lauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) methyl (meth) acrylate.
- sulfonic acid group-containing monomer examples include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) ) Acryloyloxynaphthalene sulfonic acid.
- amide monomer include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, and N-methylolpropane (meth) acrylamide.
- Examples of the (meth) acrylic acid alkylamino monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate.
- Examples of maleimide monomers include N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide.
- Examples of the vinyl monomer include vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N-vinylcarboxylic acid amides, styrene, and ⁇ -methylstyrene, and N-vinylcaprolactam.
- Examples of the cyanoacrylate monomer include acrylonitrile and methacrylonitrile.
- Examples of the epoxy group-containing acrylic monomer include glycidyl (meth) acrylate.
- polyfunctional monomers examples include hexanediol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and pentaerythritol di (meth) acrylate.
- one type of copolymerizable monomer may be used, or two or more types of copolymerizable monomers may be used.
- the acrylic polymer as described above can be obtained by polymerizing raw material monomer components.
- the polymerization technique include solution polymerization, emulsion polymerization, and bulk polymerization.
- solution polymerization for example, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, esters, and ketones can be used as a solvent.
- a polymerization initiator can be used when polymerizing the raw material monomer component to obtain an acrylic polymer.
- a photopolymerization initiator or a thermal polymerization initiator can be used.
- a chain transfer material may be used when the raw material monomer component is polymerized in order to obtain an acrylic polymer.
- an inorganic foaming agent and an organic foaming agent can be used.
- the inorganic foaming agent include water, ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and graphite.
- the organic foaming agent include chlorofluoroalkanes, azo compounds, hydrazine compounds, semicarbazide compounds, triazole compounds, and N-nitroso compounds.
- the fluorinated alkane include trichloromonofluoromethane and dichloromonofluoromethane.
- Examples of the azo compound include azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate.
- Examples of the hydrazine-based compound include p-toluenesulfonyl hydrazide, diphenylsulfone-3,3′-disulfonylhydrazide, 4,4′-oxybis (benzenesulfonylhydrazide), and allylbis (sulfonylhydrazide).
- Examples of the semicarbazide compounds include ⁇ -toluylenesulfonyl semicarbazide and 4,4′-oxybis (benzenesulfonyl semicarbazide).
- Examples of the triazole-based compound include 5-morpholyl-1,2,3,4-thiatriazole.
- Examples of the N-nitroso compound include N, N′-dinitrosopentamethylenetetramine and N, N′-dimethyl-N, N′-dinitrosotephthalamide.
- the above-mentioned thermal expansion agent that can be expanded by heating includes a component that is gasified by heating, and a thermally expandable microscopic material that includes a shell that can encapsulate the component and expand and / or break by gasification of the component. It is preferable to use a sphere.
- the heat-expandable microsphere has a configuration in which a substance such as a low boiling point liquid that can be easily gasified and expanded by heating is enclosed in an elastic shell. Examples of the substance enclosed in the shell include isobutane, propane, and pentane.
- the shell is formed of, for example, a hot-melt material that can be melted by heating to expand and / or foam the thermal expansion agent, and a material and thickness that can be expanded or broken by heat expansion or gasification of the encapsulated material. Is done.
- the material for forming the shell include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.
- Thermally expandable microspheres can be produced by, for example, a coacervation method or an interfacial polymerization method.
- the average particle size of the thermally expandable microspheres as described above is, for example, 5 to 100 ⁇ m.
- the volume expansion ratio of the thermally expandable microspheres is, for example, 5 times or more, preferably 7 times or more, more preferably 10 It is more than double.
- the content of the heat-expandable microspheres in the pressure-sensitive adhesive layer 11 is, for example, 5 to 200 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive.
- the pressure-sensitive adhesive layer 11 may contain other components in addition to the components described above.
- other components include crosslinking agents, tackifiers, plasticizers, softeners, fillers, anti-aging agents, silane coupling agents, surfactants, and colorants such as pigments and dyes. . The same may be said about the other adhesive layer mentioned later about including these components.
- the thickness of the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet X1 is preferably 1 to 1000 ⁇ m from the viewpoint of realizing good pressure-sensitive adhesiveness in the pressure-sensitive adhesive layer 11.
- the lower limit of the thickness of the pressure-sensitive adhesive layer 11 is more preferably 3 ⁇ m, more preferably 5 ⁇ m, and more preferably 8 ⁇ m.
- the upper limit of the thickness of the pressure-sensitive adhesive layer 11 is more preferably 500 ⁇ m, more preferably 100 ⁇ m, and more preferably 30 ⁇ m. About the thickness range of such an adhesive layer, it is the same also in the other adhesive layer mentioned later.
- the 180 ° peeling adhesive force (with respect to SUS304 plate, It is preferable that the tensile speed is 300 mm / min and the peeling temperature is 23 ° C.) set to 0.1 N / 10 mm or more.
- the 180 ° peel adhesive strength can be measured according to JIS Z 0237. The same applies to the adhesive strength of the other adhesive strength-reducible layers described below before the adhesive strength-lowering measure and the adhesive strength of the adhesive layer described later that is not the adhesive-reducible layer.
- the pressure-sensitive adhesive layer 11 that is a heat-peelable pressure-sensitive adhesive layer (layer capable of reducing the pressure-sensitive adhesive strength) in the pressure-sensitive adhesive sheet X1 contains a thermal expansion agent that can expand and / or foam by heating, and can reduce the pressure-sensitive adhesiveness caused by heating.
- a composition that contains a component that crystallizes by heating and can reduce the adhesive strength due to heating, and melts by heating to reduce the cohesive strength of the adhesive bulk contains a component that causes a crosslinking reaction or a curing reaction when heated.
- the pressure-sensitive adhesive layer 12 of the pressure-sensitive adhesive sheet X1 includes a pressure-sensitive adhesive as a main ingredient and has a pressure-sensitive adhesive surface 12a.
- the main agent is a component occupying the largest mass ratio among the constituent components.
- Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 12 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide. Type adhesives and urethane type adhesives. From the viewpoint of good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 12, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 12.
- the pressure-sensitive adhesive layer 12 may have a multilayer structure composed of a plurality of pressure-sensitive adhesive layers having different compositions.
- the pressure-sensitive adhesive sheet X1 may have a laminated structure including other layers in addition to the base material S1 and the pressure-sensitive adhesive layers 11 and 12 described above.
- Examples of the other layer include an undercoat layer for increasing the adhesive force between the substrate S1 and the heat-peelable pressure-sensitive adhesive layer 11.
- Examples of the constituent material of the undercoat layer include synthetic rubber and synthetic resin having rubber elasticity.
- Examples of the synthetic rubber include nitrile synthetic rubber, diene synthetic rubber, and acrylic synthetic rubber.
- the synthetic resin having rubber elasticity include polyolefin resin, polyester resin, thermoplastic elastomer, ethylene-vinyl acetate copolymer, polyurethane, polybutadiene, and soft polyvinyl chloride.
- the thickness of the undercoat layer is, for example, 0.1 to 100 ⁇ m.
- the configuration in which such an undercoat layer is provided between the base material S1 and the pressure-sensitive adhesive layer 11 is suitable for causing a pressure-sensitive adhesive force decrease in the pressure-sensitive adhesive layer 11 on the pressure-sensitive adhesive surface 11a.
- the configuration in which the undercoat layer is not provided between the substrate S1 and the pressure-sensitive adhesive layer 11 and the configuration in which the release treatment is performed on the surface of the pressure-sensitive adhesive layer 11 in the substrate S1 are the same in the pressure-sensitive adhesive layer 11. It is suitable for causing a decrease in adhesive strength due to heating on the substrate S1 side surface.
- the adhesive sheet X1 as described above can be manufactured, for example, as follows. First, the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 11 (first pressure-sensitive adhesive composition) and the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer 12 (second pressure-sensitive adhesive composition) are respectively prepared. .
- the first pressure-sensitive adhesive composition contains at least a pressure-sensitive adhesive and a thermal expansion agent.
- the second pressure-sensitive adhesive composition contains at least a pressure-sensitive adhesive.
- a first pressure-sensitive adhesive composition layer is formed by applying a first pressure-sensitive adhesive composition on a first release liner or release film whose surface has been subjected to a release treatment, and then the layer Dry. Thereby, the adhesive layer 11 is formed on the first release liner.
- the layer is dry. Thereby, the adhesive layer 12 is formed on the second release liner. Then, the pressure-sensitive adhesive layer 11 is bonded to one surface side of the base material S1, and the pressure-sensitive adhesive layer 12 is bonded to the other surface side of the base material S1. Thereafter, if necessary, the pressure-sensitive adhesive layers 11 and 12 are further dried or a crosslinking reaction is allowed to proceed.
- preparation of the pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer to be formed preparation of the pressure-sensitive adhesive composition for the pressure-sensitive adhesive layer to be formed, formation of the pressure-sensitive adhesive composition layer from the composition, from the pressure-sensitive adhesive composition layer It can be manufactured through the formation of the desired pressure-sensitive adhesive layer and the bonding of the pressure-sensitive adhesive layer to a substrate.
- the pressure-sensitive adhesive sheet X1 manufactured as described above covers a separator (release liner) or a surface of the pressure-sensitive adhesive layer 12 (pressure-sensitive adhesive surface 12a) provided to cover the surface of the pressure-sensitive adhesive layer 11 (pressure-sensitive adhesive surface 11a). It may take the form wound by roll shape with the separator (release liner) provided so that it may do.
- the adhesive sheet X1 may be provided with a pair of separators (release liners) so as to cover the adhesive surfaces 11a and 12a. The separator is peeled off from the adhesive sheet X1 when the adhesive sheet X1 is bonded to the adherend.
- a release liner it is the same also about the adhesive sheet for modeling stages which concerns on below-mentioned embodiment.
- the adhesive sheet X1 is used in a modeling stage 100 included in a layered modeling apparatus for forming a modeled object, for example, as shown in FIG. Specifically, before the formation of the modeled object, the pressure-sensitive adhesive sheet X1 is bonded to the modeled object forming surface 101 of the modeling stage 100 as shown in FIG. The pressure-sensitive adhesive sheet X1 is bonded to the modeled object forming surface 101 via the pressure-sensitive adhesive layer. Specifically, the pressure-sensitive adhesive layer X side or the pressure-sensitive adhesive layer 12 side of the pressure-sensitive adhesive sheet X1 is bonded to the modeled object forming surface 101. Is done.
- a predetermined process corresponding to the additive manufacturing technique employed in the additive manufacturing apparatus is performed, and as shown in FIG. 2B, modeling with the adhesive sheet X1 is performed on the surface.
- a target shaped object W is gradually formed on the stage 100.
- additive manufacturing techniques include a hot melt laminating method, an ink jet method, an optical modeling method, and a sheet laminating method.
- the pressure-sensitive adhesive sheet X1 is adhered to the modeled object forming surface 101 of the modeling stage 100, and the modeled object W being formed is fixed to the pressure-sensitive adhesive sheet X1 on the modeling stage 100.
- the measure for reducing the adhesive strength is heating of the adhesive layer 11 which is a layer capable of reducing the adhesive strength of the adhesive sheet X1.
- the heating temperature is, for example, a temperature at which the thermal expansion agent in the pressure-sensitive adhesive layer 11 can expand and / or foam and is 70 to 200 ° C.
- the adhesive strength of the pressure-sensitive adhesive layer 11 is reduced, and the fixed state of the model W with respect to the modeling stage 100 via the adhesive sheet X1 is released. As a result, it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X1 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 11 side before the formation of the molded article, the pressure-sensitive adhesive layer 11 has a pressure-sensitive adhesive layer 11 whose adhesive strength has decreased due to heating, for example, the pressure-sensitive adhesive layer X1. With the operation of peeling from the modeling stage 100 on the surface 11a, it becomes possible to remove the modeled object W from the modeling stage 100.
- the molded article W is formed on the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet X1 and is heated.
- the modeled object W can be removed from the modeling stage 100 by pulling the modeled object W away from the pressure-sensitive adhesive layer 11 whose adhesive strength has decreased.
- the pressure-sensitive adhesive sheet X1 for the modeling stage is fixed on the modeling stage 100 during modeling and the modeling stage after modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus. It is suitable for facilitating removal from above 100.
- a pressure-sensitive adhesive sheet X1 is used as described above when forming the modeled object W by the layered modeling apparatus, a scraper or the like having a sharp tip is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, the use of the pressure-sensitive adhesive sheet X ⁇ b> 1 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W or the modeled stage 100 when the modeled object W is removed from the modeled stage 100.
- FIG. 3A shows an adhesive sheet X1a which is a modification of the adhesive sheet X1 for the modeling stage shown in FIG.
- the pressure-sensitive adhesive sheet X1a is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 11 and 11, and includes the heat-peelable pressure-sensitive adhesive layer 11 in place of the pressure-sensitive adhesive layer 12 as described above.
- FIG. 3B shows an adhesive sheet X1b which is a modification of the pressure-sensitive adhesive sheet X1 for the modeling stage.
- the pressure-sensitive adhesive sheet X1b is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layer 11, and is different from the pressure-sensitive adhesive sheet X1 in that the pressure-sensitive adhesive layer 12 is not provided.
- the pressure-sensitive adhesive sheet X1b is used with its pressure-sensitive adhesive layer 11 side adhered to the molded object forming surface 101 of the modeling stage 100.
- the stage side end surface of the modeled object that is layered by the additive manufacturing apparatus can be fused and fixed to the modeled surface, for example, it is possible to use an adhesive sheet X1b that does not have an adhesive layer on the modeled object side. It is.
- FIG.3 (c) represents the adhesive sheet X1c which is one modification of the adhesive sheet X1 for modeling stages.
- the pressure-sensitive adhesive sheet X1c is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the pressure-sensitive adhesive layers 11 and 12, and is different from the above-described pressure-sensitive adhesive sheet X1 in that the base material S1 is not provided.
- the pressure-sensitive adhesive sheet X1c is used with its pressure-sensitive adhesive layer 11 side or pressure-sensitive adhesive layer 12 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- FIG.3 (d) represents the adhesive sheet X1d which is one modification of the modeling sheet adhesive sheet X1.
- the pressure-sensitive adhesive sheet X1d is a double-sided pressure-sensitive adhesive sheet composed of a heat-peelable pressure-sensitive adhesive layer 11, and differs from the above-described pressure-sensitive adhesive sheet X1 in that the base material S1 and the pressure-sensitive adhesive layer 12 are not provided.
- the pressure-sensitive adhesive sheet for modeling stage there may be a case where sufficient breaking strength for the pressure-sensitive adhesive sheet for modeling stage can be ensured without the base material S ⁇ b> 1 and the pressure-sensitive adhesive layer 12.
- a configuration in which the base material S1 and the pressure-sensitive adhesive layer 12 are not provided may be employed.
- These modeling stage pressure-sensitive adhesive sheets X1a, X1b, X1c, and X1d can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X1, and thus are formed on the modeling stage 100 included in the additive manufacturing apparatus.
- the molded object W to be formed is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- FIG. 4 is a partial cross-sectional view of the pressure-sensitive adhesive sheet X2 which is a pressure-sensitive adhesive sheet for modeling stage according to one embodiment of the present invention.
- the pressure-sensitive adhesive sheet X2 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 21 and 22.
- the pressure-sensitive adhesive layer 21 of the pressure-sensitive adhesive sheet X2 is a cooling peelable pressure-sensitive adhesive layer (adhesive strength-reducible layer) that can reduce the pressure-sensitive adhesive force due to cooling (adhesive strength reduction measure), and has a pressure-sensitive adhesive surface 21a.
- the pressure-sensitive adhesive layer 21 which is a cooling peelable pressure-sensitive adhesive layer is made of a pressure-sensitive adhesive composition whose adhesive strength is significantly reduced by cooling from room temperature, for example.
- the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer 21 is the present embodiment. Then, it contains a side chain crystalline polymer as an adhesive as the main agent or in addition to the adhesive as the main agent.
- the adhesive strength of the adhesive layer 21 is, for example, 6.5 N at ⁇ 30 ° C.
- Such a cooling peelable pressure-sensitive adhesive layer is, for example, a linear or branched alkyl group having 10 to 13 carbon atoms (meth) acrylic as described in JP2013-173912A.
- a pressure-sensitive adhesive composition containing an acrylic polymer as a polymer of a raw material monomer component containing an acid alkyl ester and the like and substantially free of a carboxy group-containing monomer, or a partial polymer of the raw material monomer component.
- examples of the coolant for cooling the cooling release pressure-sensitive adhesive layer include carbon dioxide gas and nitrogen gas cooled to ⁇ 30 to 10 ° C., water at a cooling temperature, and so-called antifreeze. It is done.
- the pressure-sensitive adhesive layer 21 which is a cooling release type pressure-sensitive adhesive layer (adhesive strength-reducible layer) of the pressure-sensitive adhesive sheet X2 contains a side chain crystalline polymer that can be crystallized by cooling, and can reduce the pressure-sensitive adhesive force due to cooling.
- a configuration in which the reduction can be realized may be employed.
- the adhesive layer 21 the some structure selected from these may be combined and employ
- the pressure-sensitive adhesive layer 22 of the pressure-sensitive adhesive sheet X2 includes a pressure-sensitive adhesive as a main agent and has a pressure-sensitive adhesive surface 22a.
- Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 22 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide. Type adhesives and urethane type adhesives. From the viewpoint of achieving good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 22, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 22.
- the pressure-sensitive adhesive layer 22 may have a multilayer structure including a plurality of pressure-sensitive adhesive layers having different compositions.
- the adhesive sheet X2 is used in the modeling stage 100 included in the layered manufacturing apparatus for forming a modeled object, for example, as shown in FIG. Specifically, before the formation of the modeled object, the adhesive sheet X2 is bonded to the modeled object forming surface 101 of the modeling stage 100 as shown in FIG. The pressure-sensitive adhesive sheet X2 is bonded to the modeled object forming surface 101 via the pressure-sensitive adhesive layer. Specifically, the pressure-sensitive adhesive layer X side or the pressure-sensitive adhesive layer 22 side of the pressure-sensitive adhesive sheet X2 is bonded to the modeled object forming surface 101. Is done. In the molded object formation process at the time of operation of the apparatus, as shown in FIG.
- the target molded object W is gradually formed on the modeling stage 100 with the adhesive sheet X2 on the surface.
- the modeled object W being formed is in a state of being fixed to the modeling stage 100 via the adhesive sheet X2.
- finish of a molded article formation process as shown in FIG.2 (c) the adhesive force reduction measure is performed with respect to the adhesive sheet X2 on the modeling stage 100.
- the adhesive strength reduction measure is cooling of the adhesive layer 21 which is a layer capable of reducing the adhesive strength of the adhesive sheet X2. Examples of the cooling method include supply of the coolant to the pressure sensitive adhesive sheet X2 or the pressure sensitive adhesive layer 21 by spraying.
- the cooling temperature is, for example, a temperature at which the side chain crystalline polymer in the pressure-sensitive adhesive layer 21 is crystallized, and is ⁇ 60 to ⁇ 20 ° C. Due to such cooling as a measure for reducing the adhesive strength, the adhesive strength of the pressure-sensitive adhesive layer 21 is reduced, and the fixing state of the model W with respect to the modeling stage 100 via the adhesive sheet X2 is released. As a result, it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X2 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 21 side before the formation of the molded article, for example, the pressure-sensitive adhesive layer 21 whose pressure-sensitive adhesive strength has decreased due to cooling, for example, the pressure-sensitive adhesive layer X2.
- the modeled object W With the operation of peeling from the modeling stage 100 on the surface 21a, it becomes possible to remove the modeled object W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X2 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 22 side before the formation of the molded object, the molded object W is formed on the pressure-sensitive adhesive layer 21 of the pressure-sensitive adhesive sheet X2.
- the modeled object W can be removed from the modeling stage 100 by separating the modeled object W from the pressure-sensitive adhesive layer 21 whose adhesive force has decreased.
- the modeling sheet pressure-sensitive adhesive sheet X2 is fixed on the modeling stage 100 during modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus, and after modeling, the modeling stage. It is suitable for facilitating removal from above 100.
- a pressure-sensitive adhesive sheet X2 is used as described above when forming a modeled object W by the layered modeling apparatus, a scraper having a sharp tip or the like is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, the use of the pressure-sensitive adhesive sheet X2 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W and the modeled stage 100 when the modeled object W is removed from the modeled stage 100.
- FIG. 5A shows an adhesive sheet X2a which is a modification of the modeling stage adhesive sheet X2 shown in FIG.
- the pressure-sensitive adhesive sheet X2a is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 21 and 21, and the above-mentioned pressure-sensitive adhesive sheet is provided with a cooling release type pressure-sensitive adhesive layer 21 instead of the pressure-sensitive adhesive layer 22.
- FIG. 5B shows an adhesive sheet X2b which is a modified example of the adhesive sheet X2 for the modeling stage.
- the pressure-sensitive adhesive sheet X2b is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layer 21, and is different from the pressure-sensitive adhesive sheet X2 in that the pressure-sensitive adhesive layer 22 is not provided.
- a pressure-sensitive adhesive sheet X2b is used with its pressure-sensitive adhesive layer 21 side adhered to the molded object forming surface 101 of the modeling stage 100.
- the stage side end surface of a modeled object that is layered and modeled by the layered modeling apparatus can be fused and fixed to the modeled object forming surface, for example, it is possible to use an adhesive sheet X2b that does not have an adhesive layer on the modeled object side. It is.
- FIG.5 (c) represents the adhesive sheet X2c which is one modification of the adhesive sheet X2 for modeling stages.
- the pressure-sensitive adhesive sheet X2c is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the pressure-sensitive adhesive layers 21 and 22, and is different from the above-described pressure-sensitive adhesive sheet X2 in that the base material S1 is not provided.
- the pressure-sensitive adhesive sheet X2c is used with its pressure-sensitive adhesive layer 21 side or pressure-sensitive adhesive layer 22 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- FIG.5 (d) represents the adhesive sheet X2d which is one modification of the adhesive sheet X2 for modeling stages.
- the pressure-sensitive adhesive sheet X2d is a double-sided pressure-sensitive adhesive sheet composed of a cooling and peeling type pressure-sensitive adhesive layer 21, and is different from the above-described pressure-sensitive adhesive sheet X2 in that the base material S1 and the pressure-sensitive adhesive layer 22 are not provided.
- modeling stage pressure-sensitive adhesive sheets X2a, X2b, X2c, and X2d can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X2, and thus are formed on the modeling stage 100 included in the additive manufacturing apparatus.
- the molded object W to be formed is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- FIG. 6 is a partial cross-sectional view of an adhesive sheet X3 which is an adhesive sheet for modeling stage according to an embodiment of the present invention.
- the pressure-sensitive adhesive sheet X3 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 31 and 32.
- the pressure-sensitive adhesive layer 31 of the pressure-sensitive adhesive sheet X3 is an electromagnetic wave peelable pressure-sensitive adhesive layer (adhesive strength-reducible layer) whose adhesive strength can be reduced due to irradiation of electromagnetic waves such as ultraviolet rays (adhesive strength reduction measure). It has surface 31a.
- the pressure-sensitive adhesive layer 31 is made of a pressure-sensitive adhesive composition that is cured by irradiation with electromagnetic waves.
- the pressure-sensitive adhesive composition or the pressure-sensitive adhesive layer 31 contains a pressure-sensitive adhesive polymer and an electromagnetic wave curable component.
- the electromagnetic wave curable component is, for example, a monomer or an oligomer that can start and advance a curing reaction upon irradiation with electromagnetic waves.
- the pressure-sensitive adhesive layer 31 When the pressure-sensitive adhesive layer 31 is irradiated with electromagnetic waves while the pressure-sensitive adhesive surface 31a is attached to the adherend, the reaction of the electromagnetic wave curable component induced by the irradiation proceeds in the pressure-sensitive adhesive layer 31, and the pressure-sensitive adhesive.
- the layer 31 is cured and contracted, and a shearing force is generated at the interface between the pressure-sensitive adhesive layer 31 and the adherend.
- the pressure-sensitive adhesive layer 31 is configured to reduce the pressure-sensitive adhesive force to the adherend by using the shearing force generated in this way at the interface with the adherend.
- the content of the electromagnetic wave curable component in the pressure-sensitive adhesive layer 31 is, for example, 5 to 500 parts by weight, preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the pressure-sensitive adhesive polymer in the pressure-sensitive adhesive layer 31. More preferably, it is 10 to 100 parts by mass.
- the pressure-sensitive adhesive layer 31 which is an electromagnetic wave peeling type pressure-sensitive adhesive layer (adhesive force-reducible layer) in the pressure-sensitive adhesive sheet X3 contains an electromagnetic wave curable oligomer that starts and advances a curing reaction by receiving electromagnetic wave irradiation, and is caused by electromagnetic wave irradiation.
- photocatalytic reaction is induced by receiving electromagnetic wave irradiation, and gas is generated to contain components such as azo compound and azide compound that can foam and electromagnetic wave irradiation
- gas is generated to contain components such as azo compound and azide compound that can foam and electromagnetic wave irradiation
- the pressure-sensitive adhesive layer 31 may be employed by combining a plurality of configurations selected from these. About these points regarding the structure of the adhesive layer 31, it is the same also in the adhesive layer 31 of the below-mentioned modification regarding the adhesive sheet X3.
- the pressure-sensitive adhesive layer 32 of the pressure-sensitive adhesive sheet X3 includes a pressure-sensitive adhesive as a main agent and has a pressure-sensitive adhesive surface 32a.
- the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 32 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide.
- Type adhesives and urethane type adhesives From the viewpoint of good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 32, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 32.
- the pressure-sensitive adhesive layer 32 may have a multilayer structure composed of a plurality of pressure-sensitive adhesive layers having different compositions.
- the adhesive sheet X3 is used in the modeling stage 100 included in the layered modeling apparatus for forming a modeled object, for example, as shown in FIG. 2, as with the adhesive sheet X1. Specifically, the adhesive sheet X3 is bonded to the modeling object forming surface 101 of the modeling stage 100 as shown in FIG. The pressure-sensitive adhesive sheet X3 is bonded to the modeled object forming surface 101 through the pressure-sensitive adhesive layer. Specifically, the pressure-sensitive adhesive layer X side or the pressure-sensitive adhesive layer 32 side of the pressure-sensitive adhesive sheet X3 is bonded to the modeled object forming surface 101. Is done. In the molded object formation process at the time of operation of the apparatus, as shown in FIG.
- the target molded object W is gradually formed on the modeling stage 100 with the adhesive sheet X3 on the surface.
- the modeled object W being formed is fixed to the modeling stage 100 via the adhesive sheet X3.
- finish of a molded article formation process as shown in FIG.2 (c) the adhesive force reduction measure is performed with respect to the adhesive sheet X3 on the modeling stage 100.
- the measure for reducing the adhesive strength is irradiation of electromagnetic waves with respect to the adhesive layer 31 which is a layer capable of reducing the adhesive strength of the adhesive sheet X3.
- the pressure-sensitive adhesive layer 31 When the pressure-sensitive adhesive layer 31 is subjected to the electromagnetic wave irradiation, for example, a chemical reaction induced by the irradiation proceeds in the pressure-sensitive adhesive layer 31, the pressure-sensitive adhesive layer 31 is cured and contracted, and the pressure-sensitive adhesive layer 31 and the coated layer are covered. A shearing force is generated at the interface with the adherend, and the adhesive force of the adhesive layer 31 to the adherend is reduced. In this way, the fixed state of the model W with respect to the modeling stage 100 via the adhesive sheet X3 is released. As a result, it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X3 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 31 side before the formation of the molded object, for example, the pressure-sensitive adhesive layer 31 of the pressure-sensitive adhesive layer 31 whose adhesive strength has decreased due to electromagnetic wave irradiation. With the operation of peeling from the modeling stage 100 on the adhesive surface 31a, it becomes possible to remove the modeled object W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X3 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 32 side before the formation of the molded object, the molded object W is formed on the pressure-sensitive adhesive layer 31 of the pressure-sensitive adhesive sheet X3. Therefore, the modeled object W can be removed from the modeling stage 100 by pulling the modeled object W away from the pressure-sensitive adhesive layer 31 whose adhesive force has decreased.
- the pressure-sensitive adhesive sheet X3 for the modeling stage is fixed on the modeling stage 100 during modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus, and after modeling, the modeling stage It is suitable for facilitating removal from above 100.
- a scraper or the like having a sharp tip is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, use of the pressure-sensitive adhesive sheet X3 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W or the modeled stage 100 when the modeled object W is removed from the modeled stage 100.
- FIG. 7A shows an adhesive sheet X3a which is a modification of the modeling stage adhesive sheet X3 shown in FIG.
- the pressure-sensitive adhesive sheet X3a is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 31 and 31, and includes the electromagnetic wave peeling type pressure-sensitive adhesive layer 31 in place of the pressure-sensitive adhesive layer 32.
- FIG.7 (b) represents the adhesive sheet X3b which is one modification of the adhesive sheet X3 for modeling stages.
- the pressure-sensitive adhesive sheet X3b is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layer 31, and is different from the pressure-sensitive adhesive sheet X3 described above in that the pressure-sensitive adhesive layer 32 is not provided.
- Such a pressure-sensitive adhesive sheet X3b is used with its pressure-sensitive adhesive layer 31 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- the stage side end surface of the modeled object that is layered and modeled by the layered modeling apparatus can be fused and fixed to the modeled object forming surface, for example, it is also possible to use an adhesive sheet X3b that does not have an adhesive layer on the modeled object side. It is.
- FIG.7 (c) represents the adhesive sheet X3c which is one modification of the adhesive sheet X3 for modeling stages.
- the pressure-sensitive adhesive sheet X3c is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the pressure-sensitive adhesive layers 31 and 32, and is different from the above-described pressure-sensitive adhesive sheet X3 in that the base material S1 is not provided.
- the pressure-sensitive adhesive sheet X3c is used with its pressure-sensitive adhesive layer 31 side or pressure-sensitive adhesive layer 32 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- FIG.7 (d) represents the adhesive sheet X3d which is one modification of the adhesive sheet X3 for modeling stages.
- the pressure-sensitive adhesive sheet X3d is a double-sided pressure-sensitive adhesive sheet made of an electromagnetic wave peeling type pressure-sensitive adhesive layer 31, and is different from the above-described pressure-sensitive adhesive sheet X3 in that the base material S1 and the pressure-sensitive adhesive layer 32 are not provided.
- the pressure-sensitive adhesive sheet for modeling stage can be secured without the base material S1 and the pressure-sensitive adhesive layer 32.
- a configuration in which the base material S1 and the pressure-sensitive adhesive layer 32 are not provided may be employed.
- These modeling stage pressure-sensitive adhesive sheets X3a, X3b, X3c, and X3d can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X3, and thus are formed on the modeling stage 100 included in the additive manufacturing apparatus.
- the molded object W to be formed is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- FIG. 8 is a partial cross-sectional view of the pressure-sensitive adhesive sheet X4 that is a pressure-sensitive adhesive sheet for modeling stage according to one embodiment of the present invention.
- the pressure-sensitive adhesive sheet X4 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S2 and the pressure-sensitive adhesive layers 41 and 42.
- the base material S2 is a part that functions as a support in the pressure-sensitive adhesive sheet X4 and also functions as one terminal for voltage application described later.
- the base material S2 has a laminated structure including, for example, a base main material and a conductive layer provided on the surface thereof.
- the base main material include a plastic base material, a fiber base material, and a paper base material.
- a conductive layer is a layer which has electroconductivity, for example, consists of a metal and a conductive polymer. The thickness of the conductive layer is, for example, 10 to 1000 ⁇ m. Such a conductive layer can be formed on the base main material by plating, chemical vapor deposition, or sputtering.
- the above-mentioned pressure-sensitive adhesive layer 41 is attached to the conductive layer side of the substrate S2, and the pressure-sensitive adhesive layer 41 and the conductive layer are electrically connected.
- the base material S2 of the present embodiment has an extending portion that extends and is exposed beyond the pressure-sensitive adhesive layer 41 in the surface spreading direction. In such a configuration, the electrical connection between one terminal of the voltage application device or the DC power supply device and the base material S2 or the conductive layer thereof can be easily realized via the extending portion.
- the base material S2 may be a conductive base material instead of having a laminated structure including a base main material and a conductive layer.
- Such a base material S2 is made of, for example, a metal or a conductive polymer.
- the thickness of the base material S2 having the above configuration is, for example, 10 to 1000 ⁇ m, preferably 30 to 500 ⁇ m, and more preferably 50 to 300 ⁇ m.
- the pressure-sensitive adhesive layer 41 of the pressure-sensitive adhesive sheet X4 is an electrodetachable pressure-sensitive adhesive layer (adhesive strength-reducible layer) whose adhesive strength can be reduced due to voltage application (adhesive strength reduction measure), and has an adhesive surface 41a. .
- the pressure-sensitive adhesive layer 41 contains, for example, a pressure-sensitive adhesive and an electrolyte. When a DC voltage is applied to the pressure-sensitive adhesive layer 41 so that a potential difference is generated in the thickness direction of the pressure-sensitive adhesive layer 41, the orientation of the electrolyte in the pressure-sensitive adhesive layer 41 is changed and the layer moves in the thickness direction.
- composition of the surface of the adhesive layer 41 can change, such a compositional change that occurs on the adhesive surface 11a when the adhesive layer 41 receives voltage application while the adhesive surface 41a is stuck to the adherend is utilized.
- the adhesive force of the adhesive surface 41a can be reduced.
- Examples of the adhesive contained in the adhesive layer 41 include an acrylic polymer that is an acrylic adhesive, a rubber adhesive, a vinyl alkyl ether adhesive, a silicone adhesive, a polyester adhesive, and a polyamide adhesive. , Urethane-based adhesives, fluorine-based adhesives, and epoxy-based adhesives.
- one type of pressure-sensitive adhesive may be used, or two or more types of pressure-sensitive adhesives may be used.
- the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 41 is preferably an acrylic pressure-sensitive adhesive from the viewpoint of cost reduction and high productivity.
- the composition and polymerization method of the acrylic polymer as the acrylic pressure-sensitive adhesive are the same as described above for the acrylic polymer as the acrylic pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet X1.
- the electrolyte contained in the pressure-sensitive adhesive layer 41 is a substance that can be ionized into anions and cations, and examples of such electrolytes include ionic liquids, alkali metal salts, alkaline earth metal salts, and the like. From the viewpoint of realizing good electrical peelability in the pressure-sensitive adhesive layer 41, the electrolyte contained in the pressure-sensitive adhesive layer 41 is preferably an ionic liquid.
- the ionic liquid is a salt which is liquid at room temperature (about 25 ° C.) and contains an anion and a cation.
- the anions of the ionic liquid are, for example, (CF 3 SO 2 ) 2 N ⁇ , (CF 3 CF 2 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C -, Br -, AlCl 4 -, Al 2 Cl 7 -, NO 3 -, BF 4 -, PF 6 -, CH 3 COO -, CF 3 COO -, CF 3 CF 2 CF 2 COO -, CF 3 SO It contains at least one selected from the group consisting of 3 ⁇ , CF 3 (CF 2 ) 3 SO 3 ⁇ , AsF 6 ⁇ , and SbF 6 ⁇ .
- the cation of the ionic liquid contains, for example, at least one selected from the group consisting of an imidazolium cation, a pyridinium cation, a pyrrolidinium cation, and an ammonium cation.
- Examples of commercially available ionic liquids contained in the pressure-sensitive adhesive layer 41 include “IL-A series”, “IL-P series”, “IL-C series”, “IL-IM series”, and “IL-IM series” manufactured by Guangei Chemical Industry Co., Ltd. IL-AP series ”.
- the content of the electrolyte in the pressure-sensitive adhesive layer 41 is, for example, 0.1% by mass or more in order to impart electric peelability in the pressure-sensitive adhesive layer 41.
- the content of the electrolyte in the pressure-sensitive adhesive layer 41 is preferably 0.5 parts by weight with respect to 100 parts by weight of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 41. As mentioned above, More preferably, it is 0.6 mass part or more, More preferably, it is 0.8 mass part or more, More preferably, it is 1.0 mass part or more, More preferably, it is 1.5 mass part or more.
- the electrolyte content in the pressure-sensitive adhesive layer 41 is preferably relative to 100 parts by weight of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 41. Is 30 parts by mass or less, more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
- the pressure-sensitive adhesive layer 41 as the electrodetachable pressure-sensitive adhesive layer (adhesive force-reducible layer) in the pressure-sensitive adhesive sheet X4
- an electrolyte that can be unevenly distributed by applying a DC voltage is contained in addition to the pressure-sensitive adhesive polymer, thereby causing the pressure-sensitive adhesive force resulting from voltage application.
- it contains charged particles and molecules that can be electrophoresed by application of a DC voltage in addition to the adhesive polymer, making it possible to achieve a reduction in adhesion due to voltage application.
- a low molecular weight liquid crystal component having electric field responsiveness in addition to the pressure-sensitive adhesive polymer can be phase-separated by applying an alternating voltage, and a reduction in pressure-sensitive adhesive force can be realized.
- a configuration may be employed.
- the some structure selected from these may be combined and employ
- the pressure-sensitive adhesive layer 42 of the pressure-sensitive adhesive sheet X4 includes a pressure-sensitive adhesive as a main agent and has a pressure-sensitive adhesive surface 42a.
- Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 42 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide. Type adhesives and urethane type adhesives. From the viewpoint of good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 42, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 42.
- the pressure-sensitive adhesive layer 42 may have a multilayer structure including a plurality of pressure-sensitive adhesive layers having different compositions.
- the adhesive sheet X4 is used in the modeling stage 100 included in the layered modeling apparatus for forming a modeled object, for example, as shown in FIG. 2, as with the adhesive sheet X1. Specifically, before the formation of the modeled object is started, the adhesive sheet X4 is bonded to the modeled object forming surface 101 of the modeling stage 100 as shown in FIG. In this embodiment, the modeled object forming surface 101 and / or modeled object have conductivity. For example, by fixing a conductive plate made of a conductive material on the surface of a modeling stage main body made of a non-conductive material or adopting a modeling stage main body made of a conductive material, the modeled object forming surface 101 having conductivity is accompanied.
- the modeling stage 100 can be used.
- the model material (modeled object forming material) supplied on the modeling stage 100 in the modeled object forming process is a conductive filler-containing resin composition
- the pressure-sensitive adhesive sheet X4 is bonded to the modeled object forming surface 101 via the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive layer 41 is attached to the modeled object forming surface 101 and the modeled object has conductivity
- the pressure-sensitive adhesive layer 42 is applied to the modeled object forming surface 101.
- the target formed object W is gradually formed on the modeling stage 100 with the adhesive sheet X4 on the surface.
- the modeled object W being formed is fixed to the modeled stage 100 via the adhesive sheet X4.
- finish of a molded article formation process as shown in FIG.2 (c) the adhesive force reduction measure is performed with respect to the adhesive sheet X4 on the modeling stage 100.
- the adhesive strength reduction measure is voltage application to the adhesive layer 41 that is a layer capable of reducing the adhesive strength of the adhesive sheet X4. Specifically, a voltage is applied to the pressure-sensitive adhesive layer 41 so that a potential difference is generated in the thickness direction.
- the application of the voltage with respect to the adhesive layer 41 is the base material S2 of the adhesive sheet X4 or its conductive layer, and the modeling stage 100 of a pair of terminals of a voltage application device or a DC power supply device. It can be performed after being electrically connected to the molded object forming surface 101.
- the shaped article has conductivity, voltage is applied to the adhesive layer 41 by electrically connecting a pair of terminals of the voltage application device or the DC power supply device to the base material S2 of the adhesive sheet X4 or the conductive layer and the shaped article. It can be done after connecting.
- the voltage application may be performed, for example, by bringing the positive electrode terminal of the voltage application device into contact with the base material S2 or the conductive layer thereof, and the negative electrode terminal being the other conductive part having conductivity.
- a model-formed surface 101 having conductivity with respect to the electro-peelable pressure-sensitive adhesive layer 41 and a modeled material having conductivity are used.
- the voltage application may be performed after electrically connecting a pair of terminals of the voltage application device to the modeled object forming surface 101 and the modeled object).
- the cation has a larger diffusion coefficient and tends to move faster than the anion.
- the positive electrode side of the pressure-sensitive adhesive layer 41 By applying a voltage in the above direction to the pressure-sensitive adhesive layer 41 containing the ionic liquid, the positive electrode side of the pressure-sensitive adhesive layer 41.
- the composition change on the negative pole side surface occurs before the composition change on the surface (uneven distribution of anions), and the pressure-sensitive adhesive layer 41 precedes the adhesive force on the molded object forming surface 101.
- the longer the voltage application time the lower the adhesive strength of the adhesive layer 41 or its adhesive surface 41a.
- the applied voltage to the pressure-sensitive adhesive layer 41 is preferably 1 to 100V.
- the voltage application time with respect to the adhesive layer 41 is, for example, within 60 seconds. Due to the voltage application as a measure for reducing the adhesive force as described above, the fixing state of the model W with respect to the modeling stage 100 via the adhesive sheet X4 is released. As a result, it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X4 is bonded to the conductive molded object forming surface 101 on the pressure-sensitive adhesive layer 11 side before the formation of the molded object, the pressure-sensitive adhesive whose adhesive force has decreased due to voltage application.
- the modeling object W can be removed from the modeling stage 100 as the adhesive layer 41 is peeled from the modeling stage 100 on the adhesive surface 41a.
- the pressure-sensitive adhesive sheet X4 for the modeling stage is fixed on the modeling stage 100 during modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus, and after modeling, the modeling stage It is suitable for facilitating removal from above 100.
- a pressure-sensitive adhesive sheet X4 is used as described above when forming the modeled object W by the layered modeling apparatus, a scraper or the like having a sharp tip is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, use of the pressure-sensitive adhesive sheet X4 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W or the modeled stage 100 when the modeled object W is removed from the modeled stage 100.
- FIG. 9A shows an adhesive sheet X4a which is a modification of the modeling stage adhesive sheet X4 shown in FIG.
- the pressure-sensitive adhesive sheet X4a is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S2 and the pressure-sensitive adhesive layers 41 and 41, and includes the above-described pressure-sensitive adhesive sheet in that an electro-peeling pressure-sensitive adhesive layer 41 is provided instead of the pressure-sensitive adhesive layer 42.
- FIG. 9B shows an adhesive sheet X4b which is a modification of the pressure-sensitive adhesive sheet X4 for the modeling stage.
- the pressure-sensitive adhesive sheet X4b is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S2 and the pressure-sensitive adhesive layer 41, and differs from the above-described pressure-sensitive adhesive sheet X4 in that the pressure-sensitive adhesive layer 42 is not provided.
- Such a pressure-sensitive adhesive sheet X4b is used with its pressure-sensitive adhesive layer 41 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- the modeling object formation surface 101 of the modeling stage 100 for the pressure-sensitive adhesive sheet X4b has conductivity.
- FIG. 9C shows an adhesive sheet X4c which is a modification of the pressure-sensitive adhesive sheet X4 for the modeling stage.
- the pressure-sensitive adhesive sheet X4c is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the pressure-sensitive adhesive layers 41 and 42, and is different from the above-described pressure-sensitive adhesive sheet X4 in that the base material S2 is not provided.
- Such pressure-sensitive adhesive sheet X4c is used by sticking the pressure-sensitive adhesive layer 41 side to the molded object forming surface 101 of the modeling stage 100 (in this case, the molded object forming surface 101 has conductivity), or The pressure-sensitive adhesive layer 42 side is used by being adhered to the molded object forming surface 101 (in this case, the molded object W formed on the pressure-sensitive adhesive sheet X4c or the pressure-sensitive adhesive layer 41 has conductivity).
- FIG.9 (d) represents the adhesive sheet X4d which is one modification of the adhesive sheet X4 for modeling stages.
- the pressure-sensitive adhesive sheet X4d is a double-sided pressure-sensitive adhesive sheet composed of an electrodetachable pressure-sensitive adhesive layer 41, and is different from the above-described pressure-sensitive adhesive sheet X4 in that the base material S2 and the pressure-sensitive adhesive layer 42 are not provided.
- the modeling object forming surface 101 of the modeling stage 100 for the pressure-sensitive adhesive sheet X4d has conductivity, and the modeling object W formed on the pressure-sensitive adhesive sheet X4d or the pressure-sensitive adhesive layer 41 has conductivity.
- modeling stage pressure-sensitive adhesive sheets X4a, X4b, X4c, and X4d can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X4, and thus are formed on the modeling stage 100 included in the additive manufacturing apparatus.
- the molded object W to be formed is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- FIG. 10 is a partial cross-sectional view of an adhesive sheet X5 that is an adhesive sheet for modeling stage according to an embodiment of the present invention.
- the pressure-sensitive adhesive sheet X5 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 51 and 52.
- the pressure-sensitive adhesive layer 51 of the pressure-sensitive adhesive sheet X5 is a liquid peeling type pressure-sensitive adhesive layer (adhesive strength-reducible layer) capable of reducing the pressure-sensitive adhesive force due to liquid supply (pressure-sensitive adhesive strength reduction measure), and has a pressure-sensitive adhesive surface 51a.
- the pressure-sensitive adhesive layer 51 that is a liquid peelable pressure-sensitive adhesive layer includes a pressure-sensitive adhesive having a high affinity with the liquid used for the pressure reduction measure, and the liquid used for the pressure reduction measure is water. Or when it is aqueous solution, a water-soluble adhesive is included.
- water-soluble pressure-sensitive adhesive examples include a water-soluble acrylic pressure-sensitive adhesive and a water-soluble polyvinyl ether pressure-sensitive adhesive.
- water-soluble acrylic pressure-sensitive adhesives include acrylic pressure-sensitive adhesives obtained by copolymerizing (meth) acrylic acid esters, carboxy group-containing (meth) acrylic monomers, and basic monomers such as N-vinylpyrrolidone. Can be mentioned.
- water-soluble polyvinyl ether pressure-sensitive adhesive include polyvinyl ether pressure-sensitive adhesives containing vinyl ethyl ether, vinyl butyl ether, and vinyl isobutyl ether as monomer units.
- the pressure-sensitive adhesive layer 51 contains a water-soluble pressure-sensitive adhesive
- the water-soluble pressure-sensitive adhesive in the pressure-sensitive adhesive layer 51 is used. At least a part of the adhesive dissolves or swells in the moisture, causing a volume change in the pressure-sensitive adhesive layer 51, deteriorating the pressure-sensitive adhesive surface 51 a, and reducing the pressure-sensitive adhesive force of the pressure-sensitive adhesive layer 51 to the adherend.
- the pressure-sensitive adhesive layer 51 in the pressure-sensitive adhesive sheet X5 which is a liquid peelable pressure-sensitive adhesive layer (layer capable of reducing the adhesive force), has a composition in which a part of the pressure-sensitive adhesive layer component dissolves or swells due to liquid supply,
- a configuration that has a composition that causes a volume change after drying after supplying the liquid and that can reduce the adhesive strength due to the liquid supply is adopted. May be. Or in the adhesive layer 51, these structures may be used together. About these points regarding the structure of the adhesive layer 51, it is the same also in the adhesive layer 51 of the below-mentioned modification regarding the adhesive sheet X5.
- the pressure-sensitive adhesive layer 52 of the pressure-sensitive adhesive sheet X5 includes a pressure-sensitive adhesive as a main ingredient and has a pressure-sensitive adhesive surface 52a.
- Examples of the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 52 include an acrylic polymer as an acrylic pressure-sensitive adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, a polyester pressure-sensitive adhesive, and a polyamide. Type adhesives and urethane type adhesives. From the viewpoint of good adhesive strength, cost reduction, and high productivity for the pressure-sensitive adhesive layer 52, an acrylic pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer 52.
- the pressure-sensitive adhesive layer 52 may have a multilayer structure including a plurality of pressure-sensitive adhesive layers having different compositions.
- the adhesive sheet X5 is used in the modeling stage 100 included in the layered modeling apparatus for forming a modeled object, for example, as shown in FIG. 2, as with the adhesive sheet X1. Specifically, the adhesive sheet X5 is bonded to the modeling object forming surface 101 of the modeling stage 100 as shown in FIG. The pressure-sensitive adhesive sheet X5 is bonded to the modeled object forming surface 101 via the pressure-sensitive adhesive layer. Specifically, the pressure-sensitive adhesive layer 51 side or the pressure-sensitive adhesive layer 52 side of the pressure-sensitive adhesive sheet X5 is bonded to the modeled object forming surface 101. Is done. In the molded object formation process at the time of operation of the apparatus, as shown in FIG.
- the target molded object W is gradually formed on the modeling stage 100 with the adhesive sheet X5 on the surface.
- the model W in the middle of formation is in a state of being fixed to the modeling stage 100 via the adhesive sheet X5.
- finish of a molded article formation process as shown in FIG.2 (c) the adhesive force reduction measure is performed with respect to the adhesive sheet X5 on the modeling stage 100.
- the measure for reducing the adhesive strength is a liquid supply to the adhesive layer 51 which is a layer capable of reducing the adhesive strength of the adhesive sheet X5.
- the pressure-sensitive adhesive layer 51 When the pressure-sensitive adhesive layer 51 is supplied with a liquid, at least a part of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 51 is dissolved or swells in the liquid, causing a volume change in the pressure-sensitive adhesive layer 51 and degrading the pressure-sensitive adhesive surface 51a. The adhesive strength of the pressure-sensitive adhesive layer 51 will be reduced. Thereby, the fixing state of the modeling object W with respect to the modeling stage 100 via the adhesive sheet X5 is cancelled
- the pressure-sensitive adhesive layer 51 of the pressure-sensitive adhesive layer 51 having a reduced adhesive force due to liquid supply is used. With the operation of peeling from the modeling stage 100 on the adhesive surface 51a, the modeled object W can be removed from the modeling stage 100.
- the pressure-sensitive adhesive sheet X5 is bonded to the modeling stage 100 on the pressure-sensitive adhesive layer 52 side before the formation of the molded object is started, the molded object W is formed on the pressure-sensitive adhesive layer 51 of the pressure-sensitive adhesive sheet X5. Therefore, the modeling object W can be removed from the modeling stage 100 by pulling the modeling object W away from the pressure-sensitive adhesive layer 51 having a reduced adhesive strength.
- the modeling sheet pressure-sensitive adhesive sheet X5 is fixed on the modeling stage 100 during modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus, and after modeling, the modeling stage It is suitable for facilitating removal from above 100.
- a scraper having a sharp tip or the like is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, the use of the pressure-sensitive adhesive sheet X5 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W or the modeling stage 100 when the modeled object W is removed from the modeling stage 100.
- FIG. 11A shows an adhesive sheet X5a which is a modification of the modeling stage adhesive sheet X5 shown in FIG.
- the pressure-sensitive adhesive sheet X5a is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layers 51 and 51, and includes the above-described pressure-sensitive adhesive layer 51 in place of the pressure-sensitive adhesive layer 52.
- FIG. 11B shows an adhesive sheet X5b which is a modification of the pressure-sensitive adhesive sheet X5 for the modeling stage.
- the pressure-sensitive adhesive sheet X5b is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S1 and the pressure-sensitive adhesive layer 51, and is different from the pressure-sensitive adhesive sheet X5 described above in that the pressure-sensitive adhesive layer 52 is not provided.
- Such a pressure-sensitive adhesive sheet X5b is used with its pressure-sensitive adhesive layer 51 side adhered to the molded object forming surface 101 of the modeling stage 100.
- FIG.11 (c) represents the adhesive sheet X5c which is one modification of the adhesive sheet X5 for modeling stages.
- the pressure-sensitive adhesive sheet X5c is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the pressure-sensitive adhesive layers 51 and 52, and is different from the above-described pressure-sensitive adhesive sheet X5 in that the base material S1 is not provided.
- Such a pressure-sensitive adhesive sheet X5c is used with its pressure-sensitive adhesive layer 51 side or pressure-sensitive adhesive layer 52 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- FIG. 11D shows an adhesive sheet X5d which is a modification of the pressure-sensitive adhesive sheet X5 for the modeling stage.
- the pressure-sensitive adhesive sheet X5d is a double-sided pressure-sensitive adhesive sheet composed of a liquid peelable pressure-sensitive adhesive layer 51, and is different from the above-described pressure-sensitive adhesive sheet X5 in that the base material S1 and the pressure-sensitive adhesive layer 52 are not provided.
- modeling stage pressure-sensitive adhesive sheets X5a, X5b, X5c, and X5d can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X5, and thus are formed on the modeling stage 100 included in the additive manufacturing apparatus.
- the molded object W to be formed is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- FIG. 12 is a partial cross-sectional view of the pressure-sensitive adhesive sheet X6 that is a pressure-sensitive adhesive sheet for modeling stage according to one embodiment of the present invention.
- the pressure-sensitive adhesive sheet X6 is a double-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S3 and the pressure-sensitive adhesive layers 61 and 62.
- the base material S3 of the pressure-sensitive adhesive sheet X6 is a part for functioning as a support in the pressure-sensitive adhesive sheet X6, and is a film-like base material (extensible base material) having extensibility.
- a film-like substrate S3 has an extensibility that exhibits an elongation at break of, for example, 300% or more, preferably 500% or more, more preferably 700% or more.
- the elongation at break can be measured in accordance with the “elongation” measurement method described in JIS K7311-1995.
- the film-like substrate S3 is, for example, a resin film, a woven film, or a non-woven film.
- examples of the constituent material of the base material S3 include polyurethane, polyolefin, polyester, and polycarbonate.
- examples of the polyurethane include ether polyurethane, ester polyurethane, and carbonate polyurethane.
- examples of the polyolefin include polyethylene, polypropylene, and ethylene-propylene copolymer.
- examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.
- the base material S3 is a polyurethane resin film containing polyurethane as a main ingredient.
- Polyurethane resin films are often made of a material that does not substantially exhibit a yield point. Therefore, the use of polyurethane resin films as the base material S3 has a relatively large elongation at break and break strength. It is suitable for realizing the base material to be shown and the pressure-sensitive adhesive sheet for modeling stage.
- a base material S3 of the pressure-sensitive adhesive sheet X6 may be made of one kind of material, or may be made of two or more kinds of materials.
- the base material S3 may be a laminate including a plurality of layers having different constituent materials.
- the surface of the base material S3 on the pressure-sensitive adhesive layer 61 side and / or the pressure-sensitive adhesive layer 62 side is subjected to a surface treatment for improving the adhesion with the adjacent pressure-sensitive adhesive layer.
- a surface treatment for improving the adhesion with the adjacent pressure-sensitive adhesive layer.
- Examples of such surface treatment include physical treatment such as corona treatment and plasma treatment, and chemical treatment such as undercoating treatment.
- the thickness is, for example, 10 to 300 ⁇ m.
- the pressure-sensitive adhesive layers 61 and 62 of the pressure-sensitive adhesive sheet X6 are stretch-peelable pressure-sensitive adhesive layers (layers capable of lowering the pressure-sensitive adhesive force) that can reduce the pressure-sensitive adhesive force due to stretching of the pressure-sensitive adhesive sheet X6.
- the pressure-sensitive adhesive layer 61 includes a pressure-sensitive adhesive as a main agent, and has a pressure-sensitive adhesive surface 61a for adhering to a modeling stage, for example.
- the pressure-sensitive adhesive layer 62 includes a pressure-sensitive adhesive as a main agent and has a pressure-sensitive adhesive surface 62a.
- each of the adhesive layers 61 and 62 examples include an acrylic polymer as an acrylic adhesive, natural rubber, various synthetic rubbers, a vinyl alkyl ether adhesive, a silicone adhesive, and a polyester adhesive.
- a pressure-sensitive adhesive, a polyamide-based pressure-sensitive adhesive, and a urethane-based pressure-sensitive adhesive can be mentioned. From the viewpoints of good adhesive strength, cost reduction, and high productivity for the adhesive layers 61 and 62, an acrylic adhesive is preferable as the adhesive contained in the adhesive layers 61 and 62.
- the pressure-sensitive adhesive layer 61 and / or the pressure-sensitive adhesive layer 62 may have a multilayer structure including a plurality of pressure-sensitive adhesive layers having different compositions.
- the adhesive sheet X6 is used in the modeling stage 100 included in the layered manufacturing apparatus for forming a modeled object, for example, as shown in FIG. 2, similarly to the adhesive sheet X1. Specifically, the adhesive sheet X6 is bonded to the modeling object forming surface 101 of the modeling stage 100 as shown in FIG. In the present embodiment, the pressure-sensitive adhesive layer 61 side of the pressure-sensitive adhesive sheet X6 is attached to the molded article forming surface 101. In the molded object formation process at the time of operation of the apparatus, as shown in FIG. 2B, the target molded object W is gradually formed on the modeling stage 100 with the adhesive sheet X6 on the surface.
- the modeled object W being formed is in a state of being fixed to the modeling stage 100 via the adhesive sheet X6.
- finish of a molded article formation process as shown in FIG.2 (c) the adhesive force reduction measure is performed with respect to the adhesive sheet X6 on the modeling stage 100.
- the adhesive strength reduction measure is stretching of the adhesive sheet X6. By pulling, for example, an end portion of the pressure-sensitive adhesive sheet X6 where the shaped article W is not fixed, the pressure-sensitive adhesive sheet X6 can be stretched.
- the molded object W is removed from the modeling stage 100 in accordance with the work of peeling from the modeling stage 100 on the pressure-sensitive adhesive surface 61a of the pressure-sensitive adhesive layer 61 with reduced adhesive strength. Is possible. Moreover, it becomes possible to remove the modeled object W from the modeling stage 100 by pulling the modeled object W away from the adhesive surface 62a of the pressure-sensitive adhesive layer 62 with reduced adhesive strength.
- the pressure-sensitive adhesive sheet X6 for the modeling stage is fixed on the modeling stage 100 during modeling with respect to the modeling object W formed on the modeling stage 100 included in the layered modeling apparatus, and after modeling, the modeling stage It is suitable for facilitating removal from above 100.
- a scraper having a sharp tip or the like is used to remove the modeled object W from the modeling stage 100. It is possible to avoid the use of tools. Therefore, the use of the pressure-sensitive adhesive sheet X6 for the modeling stage contributes to avoiding or suppressing damage to the modeled object W or the modeling stage 100 when the modeled object W is removed from the modeling stage 100.
- FIG. 13 shows an adhesive sheet X6a which is a modification of the pressure-sensitive adhesive sheet X6 for the modeling stage.
- the pressure-sensitive adhesive sheet X6a is a single-sided pressure-sensitive adhesive sheet having a laminated structure including the base material S3 and the pressure-sensitive adhesive layer 61, and is different from the above-described pressure-sensitive adhesive sheet X6 in that the pressure-sensitive adhesive layer 62 is not provided.
- Such a pressure-sensitive adhesive sheet X6a is used with its pressure-sensitive adhesive layer 61 side adhered to the modeling object forming surface 101 of the modeling stage 100.
- the stage side end surface of the modeled object that is layered and modeled by the layered modeling apparatus can be fused and fixed to the modeled object forming surface, for example, it is possible to use an adhesive sheet X6a that does not have an adhesive layer on the modeled object side. It is.
- Such a pressure-sensitive adhesive sheet X6a for a modeling stage can be used in the same manner as described above with respect to the pressure-sensitive adhesive sheet X6. Therefore, the molded object W formed on the modeling stage 100 included in the layered modeling apparatus. It is suitable for fixing on the modeling stage 100 during modeling and making it easy to remove from the modeling stage 100 after modeling.
- the pressure-sensitive adhesive sheet for modeling stage according to the present invention may have a magnetic peelable pressure-sensitive adhesive layer (layer capable of lowering the adhesive force) that can reduce the adhesive force due to application of a magnetic field (adhesive force reduction measure).
- a magnetic peelable pressure-sensitive adhesive layer contains, for example, a magnetic liquid such as a magnetic ionic liquid in addition to the pressure-sensitive adhesive.
- a magnetic field is applied to such a magnetic release type pressure-sensitive adhesive layer, the magnetic layer in the pressure-sensitive adhesive layer may undergo orientation change or movement, and the composition of the pressure-sensitive adhesive layer surface may change.
- the pressure-sensitive adhesive surface of the magnetic peelable pressure-sensitive adhesive layer is utilized by utilizing such a composition change that occurs on the pressure-sensitive adhesive surface. It is possible to reduce the adhesive strength.
- the pressure-sensitive adhesive sheet for modeling stage of the present invention may have a pressure-releasable pressure-sensitive adhesive layer (layer capable of reducing the adhesive strength) that can reduce the adhesive strength due to a pressure change (adhesive strength reduction measure).
- a pressure release type pressure-sensitive adhesive layer has, for example, a composition that has a composition that causes phase separation by pressurization and is capable of realizing a decrease in pressure-sensitive adhesive force due to pressurization, or foaming by pressurization or depressurization. It is possible to adopt a configuration that has a composition to be obtained and that can realize a decrease in adhesive force due to a pressure change.
- the pressure-sensitive adhesive sheet for modeling stage of the present invention includes the above-mentioned heat-peelable pressure-sensitive adhesive layer, cooling-peelable pressure-sensitive adhesive layer, electromagnetic wave-peelable pressure-sensitive adhesive layer, electro-peelable pressure-sensitive adhesive layer, liquid-peelable pressure-sensitive adhesive layer, and stretch-peelable type.
- the pressure-sensitive adhesive sheet for modeling stage of the present invention includes these heat-peelable pressure-sensitive adhesive layers, cooling-peelable pressure-sensitive adhesive layers, electromagnetic wave-peelable pressure-sensitive adhesive layers, and electro-peelable pressure-sensitive adhesive layers with or without a substrate.
- a pressure-sensitive adhesive layer for forming a stage-side pressure-sensitive adhesive layer selected from the group consisting of a liquid peelable pressure-sensitive adhesive layer, a stretch peelable pressure-sensitive adhesive layer, an electromagnetic peelable pressure-sensitive adhesive layer, and a pressure peelable pressure-sensitive adhesive layer It may have as a layer, and may have another one chosen from the group as an adhesive layer for making a modeled article side adhesion side.
- FIG. 14 is a partial configuration diagram of the additive manufacturing apparatus Y1 according to an embodiment of the present invention.
- the additive manufacturing apparatus Y1 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes an modeling stage 100 and a heating unit 110 ( Adhesive strength lowering means).
- the modeling stage 100 is made of a heat-transferable material and has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the heating unit 110 is a unit for heating the pressure-sensitive adhesive sheet for the modeling stage that is bonded to the modeling stage 100, and includes, for example, a heater 111 that is built in the modeling stage 100 and can generate heat.
- the additive manufacturing apparatus Y1 can execute an additive manufacturing technique that sequentially supplies model materials (modeled object forming materials) on the modeling stage 100 in the modeled object formation process, such as a hot melt lamination method or an inkjet method,
- the additive manufacturing apparatus Y1 further includes a supply unit (not shown) having a nozzle capable of discharging a model material. The same may be said of the additive manufacturing apparatus mentioned later about having further the supply unit which has the nozzle which can discharge a model material.
- the layered modeling apparatus Y1 it is possible to form a three-dimensional modeled object on the modeling stage 100 using the above-mentioned pressure-sensitive adhesive sheet X1 having the heat-peelable pressure-sensitive adhesive layer 11.
- the method of using the pressure-sensitive adhesive sheet X1 is as described above with reference to FIG. 2 with respect to the pressure-sensitive adhesive sheet X1, and in the formation object forming process during the operation of the layered modeling apparatus Y1, as shown in FIG.
- the molded article W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X1.
- the adhesive sheet X1 on the modeling stage 100 can be heated as a measure for reducing the adhesive force. .
- the heating unit 110 operates and generates heat after the formation of the modeled object, the heat is transmitted through the modeling stage 100 and reaches the adhesive sheet X1 or the adhesive layer 11 thereof.
- the pressure-sensitive adhesive layer 11 is subjected to the heating, the pressure-sensitive adhesive force is reduced, and the fixed state of the molded object W with respect to the modeling stage 100 via the pressure-sensitive adhesive sheet X1 is released.
- the molded article W can be removed from the modeling stage 100 as the adhesive sheet X1 is peeled at a predetermined interface formed by the adhesive layer 11 having reduced adhesive strength.
- fixing and detachment related to the modeled object W on the modeling stage 100 can be appropriately realized using the thermal peeling technique related to the adhesive layer 11 of the adhesive sheet X1. It is.
- the same technical effect can be enjoyed even when the above-mentioned pressure-sensitive adhesive sheets X1a, X1b, X1c, and X1d are used instead of the pressure-sensitive adhesive sheet X1.
- FIG. 15 is a partial configuration diagram of the additive manufacturing apparatus Y2 according to an embodiment of the present invention.
- the additive manufacturing apparatus Y2 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes an modeling stage 100 and a cooling unit 120 ( Adhesive strength lowering means).
- the modeling stage 100 has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the cooling unit 120 is a unit for cooling the modeling stage adhesive sheet bonded to the modeling stage 100, and includes a cooling pipe 121 (partially omitted) embedded in the modeling stage 100.
- the cooling pipe 121 is connected to a coolant reservoir (not shown) so that the coolant supplied from the coolant reservoir can flow therethrough.
- the coolant for example, carbon dioxide gas, nitrogen gas, water, and antifreeze can be used.
- the layered modeling apparatus Y2 it is possible to form a three-dimensional modeled object on the modeling stage 100 by using the above-mentioned pressure-sensitive adhesive sheet X2 having the cooling and peeling type pressure-sensitive adhesive layer 21.
- the method for using the adhesive sheet X2 is as described above with reference to FIG. 2 with respect to the adhesive sheet X2, and in the formation object forming process during the operation of the additive manufacturing apparatus Y2, as shown in FIG.
- the molded object W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X2.
- the adhesive sheet X2 on the modeling stage 100 can be cooled as a measure for reducing the adhesive force. .
- the cooling unit 120 operates and the coolant flows through the cooling pipe 121 after the formation of the modeled object
- the modeling stage 100 and the pressure-sensitive adhesive sheet X2 or the pressure-sensitive adhesive layer 21 are cooled and cooled.
- the pressure-sensitive adhesive layer 21 receives the cooling, the pressure-sensitive adhesive force is reduced, and the fixed state of the model W with respect to the modeling stage 100 via the pressure-sensitive adhesive sheet X2 is released.
- the usage mode of the pressure-sensitive adhesive sheet X ⁇ b> 2 it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X2 it is possible to remove the modeled object W from the modeling stage 100 as the peeling operation is performed at a predetermined interface formed by the pressure-sensitive adhesive layer 21 having reduced adhesive strength.
- fixing and detachment related to the modeled object W on the modeling stage 100 can be appropriately realized using the cooling and peeling technique related to the adhesive layer 21 of the adhesive sheet X2. It is. The same technical effect as this can also be enjoyed when the above-mentioned pressure-sensitive adhesive sheets X2a, X2b, X2c, and X2d are used instead of the pressure-sensitive adhesive sheet X2.
- FIG. 16 is a partial configuration diagram of the additive manufacturing apparatus Y3 according to one embodiment of the present invention.
- the additive manufacturing apparatus Y3 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes an modeling stage 100 and an electromagnetic wave irradiation unit 130. (Adhesive strength lowering means).
- the modeling stage 100 is made of an electromagnetic wave transmissive material, and has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the electromagnetic wave irradiation unit 130 is a unit for irradiating an electromagnetic wave to the modeling stage pressure-sensitive adhesive sheet bonded to the modeling stage 100, and includes an electromagnetic wave irradiation source that can irradiate the electromagnetic wave at a predetermined timing.
- This electromagnetic wave irradiation source is, for example, an ultraviolet lamp.
- a three-dimensional modeled object can be formed on the modeling stage 100 using the above-mentioned pressure-sensitive adhesive sheet X3 having the electromagnetic wave peeling type pressure-sensitive adhesive layer 31.
- the method of using the pressure-sensitive adhesive sheet X3 is as described above with reference to FIG. 2 with respect to the pressure-sensitive adhesive sheet X3.
- the molded object W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X3.
- the electromagnetic wave irradiation unit 130 when the electromagnetic wave irradiation unit 130 is operated after the formation of the modeled object, the electromagnetic wave is emitted from the electromagnetic wave irradiation source of the unit, and the electromagnetic wave passes through the modeling stage 100 and passes through the pressure-sensitive adhesive sheet X3 or the pressure-sensitive adhesive layer 31. Is irradiated.
- the electromagnetic wave irradiation source is an ultraviolet lamp
- ultraviolet rays pass through the modeling stage 100 and are applied to the adhesive sheet X3 or its adhesive layer 31.
- the pressure-sensitive adhesive layer 31 is irradiated with the electromagnetic wave, the pressure-sensitive adhesive force is reduced, and the fixed state of the model W with respect to the modeling stage 100 via the pressure-sensitive adhesive sheet X3 is released.
- the molded article W can be removed from the modeling stage 100 as the adhesive sheet X3 is peeled off at a predetermined interface formed by the adhesive layer 31 having reduced adhesive strength.
- the fixing and the removal regarding the modeled object W on the modeling stage 100 can be appropriately realized by using the electromagnetic wave peeling technique related to the pressure-sensitive adhesive layer 31 of the pressure-sensitive adhesive sheet X3. It is. The same technical effect as this can also be enjoyed when the above-mentioned pressure-sensitive adhesive sheets X3a, X3b, X3c, and X3d are used instead of the pressure-sensitive adhesive sheet X3.
- FIG. 17 is a partial configuration diagram of the additive manufacturing apparatus Y4 according to an embodiment of the present invention.
- the additive manufacturing apparatus Y4 is an apparatus for forming an object by an additive manufacturing technique such as a hot-melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes a modeling stage 100 and a voltage application unit 140. (Adhesive strength lowering means).
- the modeling stage 100 has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the modeling stage 100 or the modeled object forming surface 101 and / or the modeled object to be formed have conductivity.
- the voltage application unit 140 is a unit for applying a voltage to the electrodetachable pressure-sensitive adhesive layer of the modeling stage pressure-sensitive adhesive sheet bonded to the modeling stage 100, and can apply voltage at a predetermined timing. Have a good power supply.
- the voltage application unit 140 is configured such that when the modeled object forming surface 101 has conductivity, the modeled stage pressure-sensitive adhesive sheet used by being bonded to the modeled object forming surface 101 and the modeled stage 100 is an electrodetachable adhesive layer.
- the conductive part and if the modeled object has conductivity, the modeled object, through two conductive parts selected from The voltage application to the electro-peeling pressure-sensitive adhesive layer can be executed.
- FIG. 17 the case where a voltage application is performed via the molded object formation surface 101 and the electroconductive part in an adhesive sheet is illustrated.
- the layered modeling apparatus Y4 it is possible to form a three-dimensional modeled object on the modeling stage 100 by using the above-mentioned pressure-sensitive adhesive sheet X4 having the electrodetachable pressure-sensitive adhesive layer 41.
- the method of using the adhesive sheet X4 is as described above with reference to FIG. 2 with respect to the adhesive sheet X4.
- the molded object W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X4.
- the molded article W can be removed from the modeling stage 100 as the adhesive sheet X4 is peeled off at a predetermined interface formed by the adhesive layer 41 having reduced adhesive strength.
- the fixing and the removal related to the modeled object W on the modeling stage 100 can be appropriately realized by using the electric peeling technique related to the adhesive layer 41 of the adhesive sheet X4. It is.
- the same technical effect as this can also be enjoyed when the above-mentioned pressure-sensitive adhesive sheets X4a, X4b, X4c, and X4d are used instead of the pressure-sensitive adhesive sheet X4.
- FIG. 18 is a partial configuration diagram of the additive manufacturing apparatus Y5 according to one embodiment of the present invention.
- the additive manufacturing apparatus Y5 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes an modeling stage 100 and a liquid supply unit 150. (Adhesive strength lowering means).
- the modeling stage 100 has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the liquid supply unit 150 is a unit for supplying a liquid to the modeling stage pressure-sensitive adhesive sheet bonded to the modeling stage 100. In the present embodiment, the liquid supply main pipe 151 embedded in the modeling stage 100 is used. (Some are not shown).
- a side outlet hole (not shown) is formed in the wall surface of the main pipe 151, and the modeling stage 100 has a porous structure that allows the used liquid to pass from the wall surface or the side outlet hole of the main pipe 151 to the modeling object forming surface 101.
- the layered modeling apparatus Y5 it is possible to form a three-dimensional modeled object on the modeling stage 100 by using the above-mentioned pressure-sensitive adhesive sheet X5 having the liquid peelable pressure-sensitive adhesive layer 51.
- the method of using the pressure-sensitive adhesive sheet X5 is as described above with reference to FIG. 2 with respect to the pressure-sensitive adhesive sheet X5.
- the molded object W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X5.
- the liquid supply unit 150 is operated after the formation of the shaped article is completed, and a liquid capable of reducing the adhesive force of the adhesive layer 51 flows through the main pipe 151, and a part of the liquid is supplied to the side outlet of the main pipe 151.
- the main pipe 151 proceeds through the porous structure in the modeling stage 100, and reaches the pressure-sensitive adhesive sheet X 5 on the modeling stage 100 or its pressure-sensitive adhesive layer 51.
- the spray device that is the liquid supply unit 150 is operated after completion of the molding formation process, and the liquid that can reduce the adhesive force of the adhesive layer 51 is an adhesive. Spray toward the layer 51.
- the pressure-sensitive adhesive layer 51 receives the liquid supply, the adhesive strength is reduced, and the fixed state of the model W with respect to the modeling stage 100 via the pressure-sensitive adhesive sheet X5 is released.
- the usage mode of the pressure-sensitive adhesive sheet X5 it becomes easy to remove the molded article W from the modeling stage 100.
- the molded article W can be removed from the modeling stage 100 as the adhesive sheet X5 is peeled at a predetermined interface formed by the adhesive layer 51 having reduced adhesive strength.
- the fixing and the removal related to the model W on the modeling stage 100 can be appropriately realized by using the liquid peeling technique related to the adhesive layer 51 of the adhesive sheet X5. It is. The same technical effect as this can be enjoyed even when the above-mentioned pressure-sensitive adhesive sheets X5a, 5b, X5c, and X5d are used instead of the pressure-sensitive adhesive sheet X5.
- FIG. 19 is a partial configuration diagram of the additive manufacturing apparatus Y6 according to an embodiment of the present invention.
- the additive manufacturing apparatus Y6 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, or a sheet lamination method, and includes an modeling stage 100 and a stretching unit 160 ( Adhesive strength lowering means).
- the modeling stage 100 has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the stretching unit 160 is a unit for automatically stretching the modeling stage pressure-sensitive adhesive sheet bonded to the modeling stage 100.
- the layered modeling apparatus Y6 it is possible to form a three-dimensional modeled object on the modeling stage 100 using the above-described pressure-sensitive adhesive sheet X6 having the base material S3 which is an extensible base material.
- the method of using the pressure-sensitive adhesive sheet X6 is as described above with reference to FIG. 2 with respect to the pressure-sensitive adhesive sheet X6.
- the molded object W in the middle is in a state of being fixed to the modeling stage 100 via the adhesive sheet X6.
- the adhesive sheet X6 on the modeling stage 100 can be stretched as a measure for reducing the adhesive force.
- the stretching unit 160 is operated after the formation of the shaped article is completed, and the adhesive sheet X6 is automatically stretched in the surface spreading direction.
- a shearing force is generated in the stretching direction at the interface between each pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet X6 and the adherend, and the surface of the pressure-sensitive adhesive layer (adhesion) on the adherend. Surface) is released or relaxed, and the adhesive force of the adhesive surface to the adherend is reduced.
- the usage mode of the pressure-sensitive adhesive sheet X6 it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X6 it is possible to remove the molded object W from the modeling stage 100 as a result of performing an operation of peeling from the modeling stage 100 on the pressure-sensitive adhesive surface 61a of the pressure-sensitive adhesive layer 61 having reduced adhesive strength.
- the fixing and removal regarding the modeled object W on the modeling stage 100 can be appropriately realized by using the stretching and peeling technique related to the adhesive layer of the adhesive sheet X6. is there. The same technical effect as this can be enjoyed even when the above-mentioned pressure-sensitive adhesive sheet X6a is used instead of the pressure-sensitive adhesive sheet X6.
- FIG. 20 is a partial configuration diagram of the additive manufacturing apparatus Y7 according to an embodiment of the present invention.
- the additive manufacturing apparatus Y7 is an apparatus for forming an object by an additive manufacturing technique such as a hot melt lamination method, an ink jet method, an optical modeling method, a sheet lamination method, and the like, and includes a modeling stage 100 and a magnetic field application unit 170. (Adhesive strength lowering means).
- the modeling stage 100 has a modeled object forming surface 101 on which a three-dimensional modeled object is formed.
- the magnetic field application unit 170 is a unit for applying a magnetic field to the modeling stage pressure-sensitive adhesive sheet bonded to the modeling stage 100, and includes, for example, an energizable coil 171 built in the modeling stage 100.
- the layered modeling apparatus Y7 it is possible to form a three-dimensional modeled object on the modeling stage 100 using the above-mentioned pressure-sensitive adhesive sheet (the pressure-sensitive adhesive sheet X7 in FIG. 20) having a magnetic peeling type pressure-sensitive adhesive layer. is there.
- the formation object W being formed is fixed to the formation stage 100 via the adhesive sheet X7.
- the additive manufacturing apparatus Y7 is in operation, for example, after completion of the formation object forming process shown in FIG. 2C, it is possible to apply a magnetic field as a measure for reducing the adhesive force to the adhesive sheet X7 on the modeling stage 100. is there.
- the magnetic field application unit 170 operates to apply a magnetic field to the magnetic separation type pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet X7 after the formation of the shaped article is completed.
- the magnetic separation type pressure-sensitive adhesive layer is applied with a magnetic field, the adhesive force is reduced, and the fixed state of the model W with respect to the modeling stage 100 via the pressure-sensitive adhesive sheet X7 is released. As a result, it becomes easy to remove the molded article W from the modeling stage 100.
- the pressure-sensitive adhesive sheet X7 it is possible to remove the molded object W from the modeling stage 100 as a result of performing an operation of peeling at a predetermined interface formed by the magnetic peeling type pressure-sensitive adhesive layer having reduced adhesive strength.
- the fixing and removal regarding the modeled object W on the modeling stage 100 are appropriately realized by using the magnetic peeling technology related to the magnetic peeling type adhesive layer of the pressure sensitive adhesive sheet X7. Is possible.
- PET base material B1 The undercoat U1 is applied to one side of a 50 ⁇ m thick polyethylene terephthalate (PET) film (trade name “Lumirror S-10”, manufactured by Toray Industries, Inc.) and then dried to form an undercoat layer (thickness 5 ⁇ m). did. In this way, a PET substrate (PET substrate B1) having an undercoat layer formed from the undercoat U1 on one side was produced.
- PET polyethylene terephthalate
- PET base material B2 A polyethylene terephthalate (PET) film having a thickness of 50 ⁇ m (trade name “Lumirror S-10”, manufactured by Toray Industries, Inc.) was prepared as a PET base material B2.
- PET polyethylene terephthalate
- Example 1 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage>
- an isocyanate crosslinking agent trade name “Coronate L”, polyisocyanate compound, 100 parts by mass of the solid content in the solution S1 (the above acrylic polymer A1), Tosoh Corporation
- 30 parts by mass of thermally expandable microspheres trade name “Matsumoto Microsphere F-50D”, 120 ° C. expansion type, Matsumoto Yushi Seiyaku Co., Ltd.
- a composition (adhesive composition C1) for forming an agent layer was produced.
- an isocyanate-based crosslinking agent (trade name “Coronate L”, polyisocyanate is added to 100 parts by mass of the solid content in the solution S2 (the above-mentioned acrylic polymer A2) in the above-mentioned acrylic polymer solution S2.
- Compound manufactured by Tosoh Corporation
- the pressure-sensitive adhesive composition C2 is applied to the surface of the above-described PET base material B1 where the undercoat U1 is not applied (that is, the surface where the undercoat layer is not provided) to form the pressure-sensitive adhesive composition layer.
- the release film was laminated so as to cover the pressure-sensitive adhesive composition layer on the PET base material B1.
- the above-mentioned pressure-sensitive adhesive composition C1 was applied to the surface of the PET base material B1 on which the undercoat U1 was applied (that is, the surface on the undercoat layer side) to form a pressure-sensitive adhesive composition layer.
- these pressure-sensitive adhesive composition layers were dried by heating and a crosslinking reaction was caused, and a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition C2 and a thickness of 30 ⁇ m derived from the pressure-sensitive adhesive composition C1.
- a heat-peelable pressure-sensitive adhesive layer was formed.
- the heating temperature at this time is 100 ° C. and the heating time is 5 minutes.
- the pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) for the modeling stage of Example 1 having a laminated structure of [pressure-sensitive adhesive layer (non-thermally peelable) / PET base material B1 / heat-peelable pressure-sensitive adhesive layer].
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage> The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through the heat-peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. ) was pasted to the molded object forming surface of the modeling stage. Then, the 3D printer was operated to form a modeled object. Specifically, the model material is discharged and supplied from the nozzle for discharging the model material provided in the 3D printer toward the modeling stage, and a flat modeled object (100 mm) is formed on the modeling stage with the pressure-sensitive adhesive sheet for the modeling stage on the surface.
- a 3D printer trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.
- an ABS resin filament (trade name “Placil”, white color type, manufactured by Plasil) having a cross-sectional diameter of 1.75 mm was used.
- the temperature of the modeling object forming surface of the modeling stage was 90 ° C.
- the model material heating temperature inside the nozzle for discharging the model material was 240 ° C.
- the modeled object was formed in a state where it was firmly fixed on the non-thermally peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage. After finishing the molded object formation process and allowing the molded object to cool, the temperature of the molded object forming surface of the modeling stage is raised to 120 ° C.
- Example 2 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage>
- the above-mentioned acrylic polymer solution S3 and the above-mentioned acrylic polymer solution S4 and an aluminum chelate cross-linking agent (trade name “ALCH-TR”, manufactured by Kawaken Fine Chemical Co., Ltd.) are added to the above-mentioned acrylic polymer solution S3.
- Polymer A3) blended in an amount ratio such that 5 parts by mass of the solid content in the solution S4 (the above-mentioned acrylic polymer A4 as the side chain crystalline acrylic polymer) and 1 part by mass of the aluminum chelate cross-linking agent are added to 100 parts by mass.
- the composition (adhesive composition C3) for heat-peeling adhesive layer formation was produced.
- the pressure-sensitive adhesive composition C2 is applied to one surface of the above-mentioned PET base material B2 to form a pressure-sensitive adhesive composition layer, and the release film so as to cover the pressure-sensitive adhesive composition layer on the PET base material B2. Are pasted together.
- the above-mentioned pressure-sensitive adhesive composition C3 was applied to the other surface of the PET base material B2 to form a pressure-sensitive adhesive composition layer.
- these pressure-sensitive adhesive composition layers were dried by heating and a cross-linking reaction was caused, and a pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition C2 and a thickness of 30 ⁇ m derived from the pressure-sensitive adhesive composition C3. A heat-peelable pressure-sensitive adhesive layer was formed.
- the heating temperature at this time is 130 ° C. and the heating time is 3 minutes.
- the pressure-sensitive adhesive sheet double-sided pressure-sensitive adhesive sheet
- the pressure-sensitive adhesive sheet for the modeling stage of Example 2 having a laminated structure of [pressure-sensitive adhesive layer (non-thermal release type) / PET base material B2 / heat release type adhesive layer] Produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage> The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through the heat-peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. ) was pasted to the molded object forming surface of the modeling stage. Then, the 3D printer was operated to form a modeled object. Specifically, the model material is discharged and supplied from the nozzle for discharging the model material provided in the 3D printer toward the modeling stage, and a flat modeled object (100 mm) is formed on the modeling stage with the pressure-sensitive adhesive sheet for the modeling stage on the surface.
- a 3D printer trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.
- a model material a polylactic acid filament (trade name “Polyplus”, natural color type, manufactured by Polymermaker) having a cross-sectional diameter of 1.75 mm was used.
- the temperature of the modeling object forming surface of the modeling stage was 30 ° C.
- the model material heating temperature inside the nozzle for discharging the model material was 220 ° C.
- the modeled object was formed in a state where it was firmly fixed on the non-thermally peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage.
- the temperature of the molded object forming surface of the modeling stage is raised to 60 ° C. to heat the heat-peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface, and the pressure-sensitive adhesive layer
- the crystallization state of the crystalline side chain of the acrylic polymer A4 (side chain crystalline polymer) therein was released to reduce the adhesive strength of the pressure-sensitive adhesive layer.
- the fixing state via is released.) After that, for the pressure-sensitive adhesive sheet on the surface of the modeling stage, a peeling operation was performed to separate the heat-peelable pressure-sensitive adhesive layer whose adhesive strength was lowered due to heating from the surface of the modeling stage, and the molded object was removed from the modeling stage accordingly. . And the adhesive sheet was peeled off from the said molded article.
- Example 3 Provide of pressure-sensitive adhesive sheet for modeling stage> 1 part by weight of an aluminum chelate crosslinking agent (trade name “ALCH-TR”, Kawaken Fine Chemical Co., Ltd.) with respect to 100 parts by weight of the solid content (the above-mentioned acrylic polymer A5) in the solution S5 Co., Ltd.) was blended to prepare a composition for forming a cooling peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive composition C4).
- the pressure-sensitive adhesive composition C2 is applied to one surface of the above-mentioned PET base material B2 to form a pressure-sensitive adhesive composition layer, and the release film so as to cover the pressure-sensitive adhesive composition layer on the PET base material B2. Are pasted together.
- the above-mentioned pressure-sensitive adhesive composition C4 was applied to the other surface of the PET base material B2 to form a pressure-sensitive adhesive composition layer.
- these pressure-sensitive adhesive composition layers were dried by heating and caused to undergo a crosslinking reaction, so that the pressure-sensitive adhesive layer derived from the pressure-sensitive adhesive composition C2 had a thickness of 25 ⁇ m, and the pressure-sensitive adhesive composition C4 had a thickness of 30 ⁇ m.
- a cooling peelable pressure-sensitive adhesive layer was formed. The heating temperature at this time is 130 ° C. and the heating time is 3 minutes.
- the pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) for the modeling stage of Example 3 having a laminated structure of [pressure-sensitive adhesive layer (non-thermal release type) / PET base material B2 / cooling release pressure-sensitive adhesive layer] Produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage> The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories Co., Ltd.) through the cooling-peeling pressure-sensitive adhesive layer without causing wrinkles or partial lifting on the pressure-sensitive adhesive sheet. ) was pasted to the molded object forming surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage.
- BS01 + manufactured by Bonsai Laboratories Co., Ltd.
- the modeled object was formed in a state where it was firmly fixed on the non-thermally peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage. After the molded object formation process is finished and the modeled object is allowed to cool, the temperature of the modeled object forming surface of the modeling stage is lowered to 5 ° C. to cool the cooling peelable adhesive layer of the pressure-sensitive adhesive sheet on the surface, and in the pressure-sensitive adhesive layer The crystalline side chain of the acrylic polymer A5 (side chain crystalline polymer) was crystallized to reduce the adhesive strength of the pressure-sensitive adhesive layer (by this, the molded article with respect to the modeling stage was passed through the adhesive sheet. The fixing state has been released).
- Example 4 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage>
- an isocyanate crosslinking agent trade name “Coronate L”, polyisocyanate compound, 100 parts by mass of the solid content in the solution S6 (the above acrylic polymer A6), Tosoh Co., Ltd.
- a photopolymerization initiator trade name “Irgacure 651”, manufactured by BASF Corp.
- the above-mentioned pressure-sensitive adhesive composition C2 is applied to one surface of the above-mentioned PET base material B2 to form a pressure-sensitive adhesive composition layer, and the pressure-sensitive adhesive composition layer on the PET base material B2 is covered. A release film was laminated.
- the pressure-sensitive adhesive composition C5 was applied to the other surface of the PET base material B2 to form a pressure-sensitive adhesive composition layer.
- these pressure-sensitive adhesive composition layers are dried by heating and a crosslinking reaction is caused by an isocyanate cross-linking agent, and the electromagnetic wave peeling type pressure-sensitive adhesive layer having a thickness of 20 ⁇ m derived from the pressure-sensitive adhesive composition C5, and the pressure-sensitive adhesive composition An adhesive layer having a thickness of 25 ⁇ m derived from C2 was formed.
- the heating temperature at this time is 130 ° C. and the heating time is 3 minutes.
- the pressure-sensitive adhesive sheet double-sided pressure-sensitive adhesive sheet for the modeling stage of Example 4 having a laminated structure of [electromagnetic wave peelable pressure-sensitive adhesive layer / PET base material B2 / pressure-sensitive adhesive layer (non-electromagnetic wave peelable type)]. Produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, Bonsai Laboratories Co., Ltd.) through the non-electromagnetic wave peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting on the pressure-sensitive adhesive sheet. The product was bonded to the formation surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage.
- a 3D printer trade name “BS01 +”, Bonsai Laboratories Co., Ltd.
- the modeled object was formed in a state where it was firmly fixed on the electromagnetic wave peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage. After the molded object formation process is completed and the molded object is allowed to cool, the adhesive sheet on the surface of the modeling stage (having ultraviolet transparency) is irradiated with ultraviolet rays from the stage side, and the electromagnetic wave peeling type adhesive layer of the adhesive sheet The adhesion state of the modeled object with respect to the modeling stage was released through the adhesive sheet.
- This ultraviolet irradiation was performed using a high pressure mercury lamp as an ultraviolet irradiation device under irradiation conditions of an irradiation intensity of 150 mW / cm 2 with an output of 75 W and an ultraviolet irradiation integrated light quantity of 500 mJ / cm 2 .
- the modeling thing was removed from the modeling stage by pulling apart the modeling thing from the electromagnetic wave peeling type adhesive layer in which adhesive strength fell due to electromagnetic wave irradiation. After the molded object was removed, the pressure-sensitive adhesive sheet was peeled off from the surface of the modeling stage.
- Example 5 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage> 30 parts by mass of electromagnetic curable urethane acrylate (trade name “KAYARAD DPHA”, Nippon Kayaku Co., Ltd. with respect to 100 parts by mass of the solid content (the above-mentioned acrylic oligomer A7) in the above-mentioned acrylic polymer solution S7 Co., Ltd.), 5 parts by mass of an isocyanate-based crosslinking agent (trade name “Coronate L”, polyisocyanate compound, manufactured by Tosoh Corporation), and 5 parts by mass of a photopolymerization initiator (trade name “Irgacure 651”, BASF) And a composition for forming an electromagnetic wave peelable pressure-sensitive adhesive layer (pressure-sensitive adhesive composition C6).
- electromagnetic curable urethane acrylate trade name “KAYARAD DPHA”, Nippon Kayaku Co., Ltd. with respect to 100 parts by mass of the solid content (the above-mentioned acrylic oligomer A7) in
- the above-mentioned pressure-sensitive adhesive composition C2 is applied to one surface of the above-mentioned PET base material B2 to form a pressure-sensitive adhesive composition layer, and the pressure-sensitive adhesive composition layer on the PET base material B2 is covered. A release film was laminated.
- the pressure-sensitive adhesive composition C6 was applied to the other surface of the PET base material B2 to form a pressure-sensitive adhesive composition layer.
- these pressure-sensitive adhesive composition layers are dried by heating and a crosslinking reaction is caused by an isocyanate cross-linking agent, and the electromagnetic wave peeling type pressure-sensitive adhesive layer having a thickness of 20 ⁇ m derived from the pressure-sensitive adhesive composition C6, and the pressure-sensitive adhesive composition An adhesive layer having a thickness of 25 ⁇ m derived from C2 was formed.
- the heating temperature at this time is 130 ° C. and the heating time is 3 minutes.
- the pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) for Example 5 having a laminated structure of [electromagnetic wave peeling type adhesive layer / PET base material B2 / pressure sensitive adhesive layer (non-electromagnetic wave peeling type)]. Produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, Bonsai Laboratories Co., Ltd.) through the non-electromagnetic wave peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting on the pressure-sensitive adhesive sheet. The product was bonded to the formation surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage.
- a 3D printer trade name “BS01 +”, Bonsai Laboratories Co., Ltd.
- the modeled object was formed in a state where it was firmly fixed on the electromagnetic wave peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage. After the molded object formation process is finished and the molded object is allowed to cool, in the same manner as described above with respect to Example 4, UV irradiation is performed from the stage side to the pressure-sensitive adhesive sheet on the surface of the modeling stage (having ultraviolet transparency). The adhesive strength of the electromagnetic wave peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was reduced (the fixed state of the molded object with respect to the modeling stage via the pressure-sensitive adhesive sheet was thereby released).
- the modeling thing was removed from the modeling stage by pulling apart the modeling thing from the electromagnetic wave peeling type adhesive layer in which adhesive strength fell due to electromagnetic wave irradiation. After the molded object was removed, the pressure-sensitive adhesive sheet was peeled off from the surface of the modeling stage.
- Example 6 ⁇ Production of extensible substrate> 100 parts by weight of polyvinyl chloride (trade name “TH-1300”, manufactured by Shin-Etsu Chemical Co., Ltd.), 10 parts by weight of chlorinated polyethylene (trade name “Eraslen 302NA”, manufactured by Showa Denko KK), and adipic acid polyester 50 parts by mass of plasticizer (trade name “Polysizer W-2310”, manufactured by DIC Corporation), 0.5 part by mass of zinc laurate (manufactured by Mitsuwa Chemicals Co., Ltd.) as zinc soap, and alkaline earth metal soap 0.5 parts by mass of calcium stearate (made by Kishida Chemical Co., Ltd.), 2 parts by mass of hydrotalcite (trade name “Alkamizer”, manufactured by Kyowa Chemical Industry Co., Ltd.) and 2 parts by mass of black pigment A polyvinyl chloride (PVC) composition was prepared.
- PVC polyvinyl chloride
- a PVC film (thickness: 100 ⁇ m) was produced using a calendar molding machine. On one side of this PVC film, the above-mentioned undercoat U2 was applied and dried to form an undercoat layer (about 1 g / m 2 ). As described above, an extensible substrate having an undercoat layer on one side was produced.
- SBR1013 amount
- the pressure-sensitive adhesive composition C7 was applied to the surface of the stretchable substrate on the side where the undercoat layer was formed and dried to form a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m.
- a pressure-sensitive adhesive sheet (single-sided pressure-sensitive adhesive sheet) for the modeling stage of Example 6 having a laminated structure of [extensible base material / rubber-based pressure-sensitive adhesive layer] was produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage> The pressure-sensitive adhesive sheet produced as described above is formed into a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories) through the pressure-sensitive adhesive layer without causing wrinkles or partial lifting on the pressure-sensitive adhesive sheet. It stuck together on the modeling object formation surface of the stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage. The modeled object was formed in a state where it was fixed to the extensible substrate of the pressure-sensitive adhesive sheet on the surface of the modeling stage.
- BS01 + manufactured by Bonsai Laboratories
- the pressure-sensitive adhesive sheet is stretched by pulling the end of the pressure-sensitive adhesive sheet in the surface spreading direction of the pressure-sensitive adhesive sheet, and the adhesive force of the pressure-sensitive adhesive layer to the modeling stage surface is reduced. (Thus, the fixing state of the modeled object with respect to the modeling stage via the pressure-sensitive adhesive sheet was released). Thereafter, the pressure-sensitive adhesive sheet on the surface of the modeling stage was peeled off from the surface of the modeling stage to remove the pressure-sensitive adhesive layer having a reduced adhesive force, and the molded object was removed from the modeling stage. And the adhesive sheet was peeled off from the said molded article.
- Example 7 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage>
- an isocyanate crosslinking agent trade name “Coronate L”, polyisocyanate compound, 100 parts by mass of the solid content in the solution S2 (the above acrylic polymer A2), Manufactured by Tosoh Corporation
- 20 parts by mass of a tackifier trade name “Sumilite Resin PR12603”, manufactured by Sumitomo Durez Co., Ltd.
- 20 parts by mass of rosin ester trade name “Esthegam AT”, Arakawa Chemical Industries
- the adhesive composition C8 was applied and dried on both sides of a Manila hemp nonwoven substrate (thickness 50 ⁇ m, basis weight 20 g / m 2 ) to form an adhesive layer having a thickness of 55 ⁇ m.
- a pressure-sensitive adhesive sheet having a laminated structure of [pressure-sensitive adhesive layer / nonwoven fabric substrate / pressure-sensitive adhesive layer] was produced.
- 5 parts by mass of an isocyanate crosslinking agent (trade name “Coronate L”, polyisocyanate is added to 100 parts by mass of the solid content in the solution S2 (the above-mentioned acrylic polymer A2) in the acrylic polymer solution S2.
- a composition for forming a pressure-sensitive adhesive layer (adhesive composition C9) was produced.
- the pressure-sensitive adhesive composition C9 was applied to the release-treated surface of the release film obtained by subjecting one side of the 25 ⁇ m-thick polyester film to a release treatment to form a pressure-sensitive adhesive composition layer.
- the pressure-sensitive adhesive composition layer on the release film was dried by heating and a crosslinking reaction was caused to form a heat-peelable pressure-sensitive adhesive layer having a thickness of 50 ⁇ m.
- the heating temperature at this time is 100 ° C. and the heating time is 5 minutes.
- surface of the said adhesive sheet which has the adhesive layer formed from adhesive composition C8 on both surfaces, and the said heat-peeling-type adhesive layer were bonded together.
- An adhesive sheet double-sided adhesive sheet
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through the heat-peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. ) was pasted to the molded object forming surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage.
- BS01 + manufactured by Bonsai Laboratories, Inc.
- the modeled object was formed in a state where it was firmly fixed on the non-thermally peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage.
- the temperature of the molded object forming surface of the modeling stage is raised to 120 ° C. to heat the heat-peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface, and the pressure-sensitive adhesive layer
- the thermally expandable microspheres in the inside were expanded to reduce the adhesive force of the pressure-sensitive adhesive layer (the fixed state of the molded object with respect to the modeling stage via the pressure-sensitive adhesive sheet was released).
- Example 8 ⁇ Production of pressure-sensitive adhesive sheet for modeling stage>
- the pressure-sensitive adhesive composition layer is formed by applying the above-mentioned pressure-sensitive adhesive composition C5 for forming an electromagnetic wave peeling pressure-sensitive adhesive layer to one surface (the surface on which the undercoat layer is not provided) of the above-described PET base material B1. did.
- the pressure-sensitive adhesive composition layer was dried by heating, and a crosslinking reaction with an isocyanate crosslinking agent was caused to form an electromagnetic wave peelable pressure-sensitive adhesive layer having a thickness of 20 ⁇ m.
- the heating temperature at this time is 130 ° C. and the heating time is 3 minutes.
- the above-mentioned pressure-sensitive adhesive composition C9 for forming a heat-peelable pressure-sensitive adhesive layer is applied to the release-treated surface of a release film obtained by subjecting one surface of a 25 ⁇ m thick polyester film to a pressure-sensitive adhesive composition layer. Formed. Next, the pressure-sensitive adhesive composition layer on the release film was dried by heating and a crosslinking reaction was caused to form a heat-peelable pressure-sensitive adhesive layer having a thickness of 50 ⁇ m. The heating temperature at this time is 100 ° C. and the heating time is 5 minutes.
- the electromagnetic peeling type adhesive layer formed from the adhesive composition C5 is provided on the other side (side of the undercoat layer side) of the PET base material B1 with the side of the one side.
- the agent layer was bonded.
- a pressure-sensitive adhesive sheet double-sided pressure-sensitive adhesive sheet for the modeling stage of Example 8 having a laminated structure of [electromagnetic wave peelable pressure-sensitive adhesive layer / PET base material B1 / heat peelable pressure-sensitive adhesive layer] was produced.
- ⁇ Use of pressure-sensitive adhesive sheet for modeling stage The pressure-sensitive adhesive sheet produced as described above is subjected to a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through the heat-peelable pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. ) was pasted to the molded object forming surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage.
- BS01 + manufactured by Bonsai Laboratories, Inc.
- the modeled object was formed in a state where it was firmly fixed on the electromagnetic wave peelable pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage. After the molded object formation process is completed and the molded object is allowed to cool, the adhesive sheet on the surface of the modeling stage (having ultraviolet transparency) is irradiated with ultraviolet rays from the stage side, and the electromagnetic wave peeling type adhesive layer of the adhesive sheet The adhesion state of the modeled object with respect to the modeling stage was released through the adhesive sheet.
- This ultraviolet irradiation was performed using a high pressure mercury lamp as an ultraviolet irradiation device under irradiation conditions of an irradiation intensity of 150 mW / cm 2 with an output of 75 W and an ultraviolet irradiation integrated light quantity of 500 mJ / cm 2 .
- the modeling thing was removed from the modeling stage by pulling apart the modeling thing from the electromagnetic wave peeling type adhesive layer in which adhesive strength fell due to electromagnetic wave irradiation.
- the molded object forming surface of the modeling stage is heated to 120 ° C.
- the pressure-sensitive adhesive composition C11 was applied on a 38 ⁇ m-thick polyester film (peeled film) having a release treatment on the surface to form a pressure-sensitive adhesive composition layer.
- the pressure-sensitive adhesive composition layer was dried on the release film and a crosslinking reaction was caused to form a pressure-sensitive adhesive layer having a thickness of 65 ⁇ m.
- the heating temperature at this time is 100 ° C., and the heating time is 3 minutes.
- Two adhesive layers with a release film (thickness: 65 ⁇ m) were formed by such a method.
- the said adhesive layer was bonded together on each of both surfaces of the nonwoven fabric base material of Manila hemp (50 micrometers in thickness, basic weight 20g / m ⁇ 2 >).
- a pressure-sensitive adhesive sheet (double-sided pressure-sensitive adhesive sheet) of Comparative Example 1 having a laminated structure of [pressure-sensitive adhesive layer / nonwoven fabric substrate / pressure-sensitive adhesive layer] was produced.
- the pressure-sensitive adhesive sheet produced as described above is a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through one pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. It was bonded to the modeling object forming surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage. The modeled object was formed in a state of being fixed to the other pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage.
- BS01 + manufactured by Bonsai Laboratories, Inc.
- the pressure-sensitive adhesive sheet produced as described above is a 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories, Inc.) through one pressure-sensitive adhesive layer without causing wrinkles or partial lifting of the pressure-sensitive adhesive sheet. It was bonded to the modeling object forming surface of the modeling stage. Then, the 3D printer was operated under the same conditions as described above with respect to Example 1, and a flat shaped object (100 mm ⁇ 100 mm, thickness 2 mm) was formed on the modeling stage. The modeled object was formed in a state of being fixed to the other pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet on the surface of the modeling stage.
- the modeling thing was removed from the modeling stage by trying the peeling operation
- the removal of the modeled object from the modeling stage the case where the modeled object can be easily removed is evaluated as being very easy to remove ( ⁇ ). When necessary, it was evaluated as being difficult to remove ( ⁇ ), and when it was difficult to remove without using a tool such as a scraper having a sharp tip, it was evaluated as difficult to remove ( ⁇ ). The results are listed in Tables 1-3.
- the peeling force required for removal of the molded article from the modeling stage that is, the external force required to peel the adhesive sheet from the modeling stage surface with the molded article was measured.
- the pressure-sensitive adhesive sheet was bonded to a modeling object forming surface of a modeling stage of a hot melt lamination type 3D printer (trade name “BS01 +”, manufactured by Bonsai Laboratories) as a layered modeling apparatus.
- a 3D printer was operated to form a modeled object.
- an ABS resin filament (trade name “Plasil”, cross-sectional diameter 1.75 mm, white, which is a model material heated to 240 ° C. inside the nozzle from the nozzle for discharging the model material provided in the 3D printer toward the modeling stage. Color type, manufactured by Plasil Co., Ltd.) was discharged and formed, and a model was formed on the modeling stage with the pressure-sensitive adhesive sheet for the modeling stage on the surface. The temperature of the model formation surface of the modeling stage during the model formation process was 100 ° C.
- the formed object has a main body 201 and a wall 202 as shown in FIG.
- the main body 201 has a flat plate shape (100 mm ⁇ 100 mm, thickness 2 mm) that is rectangular in plan view.
- the wall portion 202 is located at the edge of the main body portion 201 and extends along the entire side of the main body portion 201, and has a height of 7 mm and a thickness of 2 mm. Moreover, the wall part 202 is a site
- the pressure-sensitive adhesive sheet is stretched by pulling the end of the pressure-sensitive adhesive sheet with a force of 4.5 kg in the surface spreading direction of the pressure-sensitive adhesive sheet, The adhesive force of the pressure-sensitive adhesive layer to the surface of the modeling stage was reduced. Then, an external force (maximum value) required to remove the model from the modeling stage by pulling the string having one end connected to the wall 202 of the model in the direction indicated by the arrow D in FIG. was measured using a push-pull gauge (trade name “PS (Max. Capacity 5 kg)”, manufactured by Imada Manufacturing Co., Ltd.) to which the other end of the string was bound. The measured value in this measurement was 0 kg weight. That is, the modeled object to be removed was substantially already removed from the modeling stage by the above-described stretching of the pressure-sensitive adhesive sheet.
- the peeling force required for removing the molded object from the modeling stage that is, the external force required for peeling with the pressure-sensitive adhesive sheet from the modeling stage surface with the molded object was measured. Specifically, the temperature of the modeling object forming surface of the modeling stage during the modeling object forming process was changed to 90 ° C. instead of 100 ° C., and as a measure for reducing the adhesive strength, heat peeling type adhesive instead of stretching the adhesive sheet The peel force was measured in the same manner as described above with respect to Example 6 except that the agent layer was heated.
- the heat-peelable pressure-sensitive adhesive layer is heated by raising the surface of the modeling stage to 120 ° C., and the heat-expandable microspheres in the heat-peelable pressure-sensitive adhesive layer are expanded by the heating.
- the adhesive strength of the agent layer was reduced.
- the measured value in this measurement was 0.05 kg weight.
- the peeling force required for removing the molded object from the modeling stage that is, the external force required for peeling with the pressure-sensitive adhesive sheet from the modeling stage surface with the molded object was measured. Specifically, the peeling force measurement was performed in the same manner as described above with respect to Example 6 except that the peeling operation was performed when the modeling stage was cooled to 30 ° C. after the formation of the molded object. The measured value in each measurement was not less than the measurement limit (5 kg weight) of the push-pull gauge used.
- the modeled object can be easily obtained from the modeling stage after the modeled object forming process is completed. Can not be removed.
- the force required for removing the modeled object measured by the measurement method described above, was not less than the measurement limit, that is, not less than 5 kg weight.
- Adhesive sheet (adhesive sheet for modeling stage) S1, S2, S3 Base material 11, 12, 21, 22, 31, 32, 41, 42, 51, 52, 61, 62 Adhesive layer 100 Modeling stage 101 Modeling object forming surface 110 Heating unit 120 Cooling unit 130 Electromagnetic wave irradiation Unit (electromagnetic wave irradiation means, adhesive strength reduction means) 140 Voltage application unit (voltage application means, adhesive strength reduction means) 150 Liquid supply unit 160 Stretching unit 170 Magnetic field applying unit
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Abstract
Description
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、60質量部のアクリル酸エチルと、30質量部のアクリル酸2-エチルヘキシルと、5質量部のメタクリル酸メチルと、5質量部のアクリル酸ヒドロキシエチルと、重合開始剤たる0.2質量部の過酸化ベンゾイルと、重合溶媒たる100質量部のトルエンとを含む混合物について、窒素ガスを導入しながら60℃にて6時間の重合反応を行った。これにより、実施例1の熱剥離型粘着剤層形成用のアクリル系ポリマー(アクリル系ポリマーA1)を含有する溶液(アクリル系ポリマー溶液S1)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、92質量部のアクリル酸ブチルと、3質量部のメタクリル酸メチルと、5質量部のアクリル酸と、重合開始剤たる0.2質量部の2,2'-アゾビスイソブチロニトリルと、重合溶媒たる100質量部の酢酸エチルとを含む混合物について、窒素ガスを導入しながら60℃にて6時間の重合反応を行った。これにより、粘着剤層形成用のアクリル系ポリマー(アクリル系ポリマーA2)を含有する溶液(アクリル系ポリマー溶液S2)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、55質量部のアクリル酸2-エチルヘキシルと、40質量部のアクリル酸メチルと、5質量部のアクリル酸2-ヒドロキシエチルと、重合開始剤たる0.2質量部の過酸化ベンゾイルと、重合溶媒たる100質量部のトルエンとを含む混合物について、窒素ガスを導入しながら60℃にて6時間の重合反応を行った。これにより、実施例2の熱剥離型粘着剤層形成用のアクリル系ポリマー(アクリル系ポリマーA3)を含有する溶液(アクリル系ポリマー溶液S3)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、40質量部のベヘニルアクリレートと、35質量部のステアリルアクリレートと、20質量部のアクリル酸メチルと、5質量部のアクリル酸と、連鎖移動剤たる5質量部のドデシルメルカプタンと、重合開始剤たる0.5質量部の過酸化ベンゾイルと、重合溶媒たる100質量部のトルエンとを含む混合物について、窒素ガスを導入しながら80℃にて6時間の重合反応を行った。これにより、実施例2の熱剥離型粘着剤層形成用の側鎖結晶性アクリル系ポリマー(アクリル系ポリマーA4)を含有する溶液(アクリル系ポリマー溶液S4)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、60質量部のベヘニルアクリレートと、35質量部のイソボニルメタクリレートと、5質量部のメタクリル酸と、重合開始剤たる0.5質量部の過酸化ベンゾイルと、重合溶媒たる100質量部の酢酸エチルとを含む混合物について、窒素ガスを導入しながら60℃にて6時間の重合反応を行った。これにより、実施例3の冷却剥離型粘着剤層形成用の側鎖結晶性アクリル系ポリマー(アクリル系ポリマーA5)を含有する溶液(アクリル系ポリマー溶液S5)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、35質量部のアクリル酸2-エチルヘキシルと、45質量部のアクリル酸ブチルと、20質量部のアクリル酸2-ヒドロキシエチルと、重合開始剤たる0.2質量部の2,2'-アゾビスイソブチロニトリルと、重合溶媒たる100質量部のトルエンとを含む混合物について、窒素ガスを導入しながら60℃にて6時間の重合反応を行ってアクリル系ポリマーA6'を得た。続いて、アクリル系ポリマーA6'を含有する当該反応溶液に20質量部の2-メタクリロイルオキシエチルイソシアネートを加え、空気雰囲気下、50℃にて48時間の付加反応を行った。これにより、実施例4の電磁波硬化型粘着剤層形成用の電磁波硬化型アクリル系ポリマー(アクリル系ポリマーA6,ポリマー分子内側鎖に炭素-炭素二重結合が導入されている)を含有する溶液(アクリル系ポリマー溶液S6)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、50質量部のアクリル酸2-エチルヘキシルと、45質量部のアクリル酸ブチルと、5質量部のアクリル酸2-ヒドロキシエチルと、重合溶媒たる100質量部のトルエンとを含む混合物について、窒素ガスを導入しながら60℃にて8時間の重合反応を行った。これにより、実施例5の電磁波剥離型粘着剤層形成用の電磁波硬化型アクリル系オリゴマー(アクリル系オリゴマーA7)を含有する溶液(アクリル系ポリマー溶液S7)を得た。
環流冷却器と、窒素ガス導入管と、攪拌機と、温度計とを備えた反応容器内で、90質量部のアクリル酸n-ブチル(BA)と、5質量部のメタクリル酸メチル(MMA)と、5質量部のアクリル酸(AA)と、重合溶媒たる186質量部の酢酸エチルとを含む混合物について、窒素ガスを導入しながら1時間の撹拌を行った。次に、このようにして重合系内の酸素を除去した後、反応容器内の溶液について、63℃で10時間の反応を行った。その後、当該溶液について冷却し、比較例1,2の粘着剤層形成用のアクリル系ポリマー(アクリル系ポリマーA8,BAとMMAとAAとの共重合体)を含有する溶液(アクリル系ポリマー溶液S8)を得た。アクリル系ポリマー溶液S8の固形分濃度は35質量%であった。
上述のアクリル系ポリマー溶液S1に、この溶液S1中の固形分(アクリル系ポリマーA1)100質量部に対して4質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)を加えて混合し、下塗り剤U1を調製した。
メタクリル酸メチルが重合してなる天然ゴム(商品名「MMAグラフト天然ゴム MG30」,マレーシアゴム研究所製)100質量部と、イソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)50質量部と、トルエン900質量部とを混合して下塗り剤U2を調製した。
厚さ50μmのポリエチレンテレフタレート(PET)フィルム(商品名「ルミラー S-10」,東レ株式会社製)の片面に、上述の下塗り剤U1を塗布した後に乾燥して下塗り層(厚さ5μm)を形成した。このようにして、下塗り剤U1から形成された下塗り層を片面に有するPET基材(PET基材B1)を作製した。
厚さ50μmのポリエチレンテレフタレート(PET)フィルム(商品名「ルミラー S-10」,東レ株式会社製)をPET基材B2として用意した。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S1に、この溶液S1中の固形分(上述のアクリル系ポリマーA1)100質量部に対して4質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)と30質量部の熱膨張性微小球(商品名「マツモトマイクロスフェアー F-50D」,120℃膨張タイプ,松本油脂製薬株式会社製)とを配合して、熱剥離型粘着剤層形成用の組成物(粘着剤組成物C1)を作製した。また、上述のアクリル系ポリマー溶液S2に、この溶液S2中の固形分(上述のアクリル系ポリマーA2)100質量部に対して5質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)を配合して、粘着剤層形成用の組成物(粘着剤組成物C2)を作製した。次に、上述のPET基材B1において下塗り剤U1が塗布されていない面(即ち、下塗り層が設けられていない側の面)に粘着剤組成物C2を塗布して粘着剤組成物層を形成し、PET基材B1上の当該粘着剤組成物層を覆うように剥離フィルムを張り合わせた。次に、PET基材B1において下塗り剤U1が塗布されている面(即ち、下塗り層側の面)に上述の粘着剤組成物C1を塗布して粘着剤組成物層を形成した。次に、これら粘着剤組成物層について加熱によって乾燥させ且つ架橋反応を生じさせて、粘着剤組成物C2由来の厚さ25μmの粘着剤層、および、粘着剤組成物C1由来の厚さ30μmの熱剥離型粘着剤層を、形成した。このときの加熱温度は100℃であり且つ加熱時間は5分間である。以上のようにして、[粘着剤層(非熱剥離型)/PET基材B1/熱剥離型粘着剤層]の積層構造を有する実施例1の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその熱剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、3Dプリンタを稼動させて造形物を形成した。具体的には、3Dプリンタの備えるモデル材吐出用ノズルから造形ステージに向けてモデル材を吐出供給して、表面に造形ステージ用の粘着シートを伴う造形ステージの上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。モデル材としては、断面直径1.75mmのABS樹脂フィラメント(商品名「プラシル」,ホワイトカラータイプ,プラシル社製)を用いた。造形物形成過程において、造形ステージの造形物形成面の温度は90℃とし、モデル材吐出用ノズルの内部でのモデル材加熱温度は240℃とした。造形物は、造形ステージ表面の粘着シートの非熱剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージの造形物形成面を120℃に昇温させて当該表面の粘着シートの熱剥離型粘着剤層を加熱し、当該粘着剤層中の熱膨張性微小球を膨張させて当該粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。その後、造形ステージ表面の粘着シートについて、加熱に因って粘着力の低下した熱剥離型粘着剤層を造形ステージ表面から離す剥離作業を行い、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S3に、上述のアクリル系ポリマー溶液S4およびアルミキレート架橋剤(商品名「ALCH-TR」,川研ファインケミカル株式会社製)を、溶液S3中の固形分(上述のアクリル系ポリマーA3)100質量部に対して溶液S4中の固形分(側鎖結晶性アクリル系ポリマーたる上述のアクリル系ポリマーA4)が5質量部およびアルミキレート架橋剤が1質量部となる量比で配合して、熱剥離型粘着剤層形成用の組成物(粘着剤組成物C3)を作製した。次に、上述のPET基材B2の一方の面に粘着剤組成物C2を塗布して粘着剤組成物層を形成し、PET基材B2上の当該粘着剤組成物層を覆うように剥離フィルムを張り合わせた。次に、PET基材B2の他方の面に上述の粘着剤組成物C3を塗布して粘着剤組成物層を形成した。次に、これら粘着剤組成物層について加熱によって乾燥させ且つ架橋反応を生じさせて、粘着剤組成物C2由来の厚さ25μmの粘着剤層、および、粘着剤組成物C3由来の厚さ30μmの熱剥離型粘着剤層を、形成した。このときの加熱温度は130℃であり且つ加熱時間は3分間である。以上のようにして、[粘着剤層(非熱剥離型)/PET基材B2/熱剥離型粘着剤層]の積層構造を有する実施例2の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその熱剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、3Dプリンタを稼動させて造形物を形成した。具体的には、3Dプリンタの備えるモデル材吐出用ノズルから造形ステージに向けてモデル材を吐出供給して、表面に造形ステージ用の粘着シートを伴う造形ステージの上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。モデル材としては、断面直径1.75mmのポリ乳酸フィラメント(商品名「Polyplus」,ナチュラルカラータイプ,Polymaker社製)を用いた。造形物形成過程において、造形ステージの造形物形成面の温度は30℃とし、モデル材吐出用ノズルの内部でのモデル材加熱温度は220℃とした。造形物は、造形ステージ表面の粘着シートの非熱剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージの造形物形成面を60℃に昇温させて当該表面の粘着シートの熱剥離型粘着剤層を加熱し、当該粘着剤層中のアクリル系ポリマーA4(側鎖結晶性ポリマー)の有する結晶性側鎖の結晶化状態を解いて当該粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。その後、造形ステージ表面の粘着シートについて、加熱に因って粘着力の低下した熱剥離型粘着剤層を造形ステージ表面から離す剥離作業を行い、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S5に、この溶液S5中の固形分(上述のアクリル系ポリマーA5)100質量部に対して1質量部のアルミキレート架橋剤(商品名「ALCH-TR」,川研ファインケミカル株式会社製)を配合して、冷却剥離型粘着剤層形成用の組成物(粘着剤組成物C4)を作製した。次に、上述のPET基材B2の一方の面に粘着剤組成物C2を塗布して粘着剤組成物層を形成し、PET基材B2上の当該粘着剤組成物層を覆うように剥離フィルムを張り合わせた。次に、PET基材B2の他方の面に上述の粘着剤組成物C4を塗布して粘着剤組成物層を形成した。次に、これら粘着剤組成物層について加熱によって乾燥させ且つ架橋反応を生じさせて、粘着剤組成物C2由来の厚さ25μmの粘着剤層、および、粘着剤組成物C4由来の厚さ30μmの冷却剥離型粘着剤層を、形成した。このときの加熱温度は130℃であり且つ加熱時間は3分間である。以上のようにして、[粘着剤層(非熱剥離型)/PET基材B2/冷却離型粘着剤層]の積層構造を有する実施例3の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその冷却剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの非熱剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージの造形物形成面を5℃に降温させて当該表面の粘着シートの冷却剥離型粘着剤層を冷却し、当該粘着剤層中のアクリル系ポリマーA5(側鎖結晶性ポリマー)の有する結晶性側鎖を結晶化させて当該粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。その後、造形ステージ表面の粘着シートについて、冷却に因って粘着力の低下した冷却剥離型粘着剤層を造形ステージ表面から離す剥離作業を行い、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S6に、この溶液S6中の固形分(上述のアクリル系ポリマーA6)100質量部に対して5質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)と5質量部の光重合開始剤(商品名「イルガキュア651」,BASF社製)とを配合して、電磁波剥離型粘着剤層形成用の組成物(粘着剤組成物C5)を作製した。次に、上述のPET基材B2の一方の面に上述の粘着剤組成物C2を塗布して粘着剤組成物層を形成し、PET基材B2上の当該粘着剤組成物層を覆うように剥離フィルムを張り合わせた。次に、PET基材B2の他方の面に粘着剤組成物C5を塗布して粘着剤組成物層を形成した。次に、これら粘着剤組成物層について加熱によって乾燥させ且つイソシアネート架橋剤による架橋反応を生じさせて、粘着剤組成物C5由来の厚さ20μmの電磁波剥離型粘着剤層、および、粘着剤組成物C2由来の厚さ25μmの粘着剤層を、形成した。このときの加熱温度は130℃であり且つ加熱時間は3分間である。以上のようにして、[電磁波剥離型粘着剤層/PET基材B2/粘着剤層(非電磁波剥離型)]の積層構造を有する実施例4の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその非電磁波剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの電磁波剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージ(紫外線透過性を有する)の表面の粘着シートに対してステージ側から紫外線照射を行い、当該粘着シートの電磁波剥離型粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。この紫外線照射は、紫外線照射装置として高圧水銀灯を使用して、出力75Wによる照射強度150mW/cm2および紫外線照射積算光量500mJ/cm2の照射条件で行った。そして、電磁波照射に因って粘着力の低下した電磁波剥離型粘着剤層から造形物を引き離すことによって、造形ステージ上から造形物を取り外した。造形物が取り外された後、造形ステージ表面から粘着シートを剥離した。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S7に、この溶液S7中の固形分(上述のアクリル系オリゴマーA7)100質量部に対して30質量部の電磁波硬化性ウレタンアクリレート(商品名「KAYARAD DPHA」,日本化薬株式会社製)と、5質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)と、5質量部の光重合開始剤(商品名「イルガキュア651」,BASF社製)とを配合して、電磁波剥離型粘着剤層形成用の組成物(粘着剤組成物C6)を作製した。次に、上述のPET基材B2の一方の面に上述の粘着剤組成物C2を塗布して粘着剤組成物層を形成し、PET基材B2上の当該粘着剤組成物層を覆うように剥離フィルムを張り合わせた。次に、PET基材B2の他方の面に粘着剤組成物C6を塗布して粘着剤組成物層を形成した。次に、これら粘着剤組成物層について加熱によって乾燥させ且つイソシアネート架橋剤による架橋反応を生じさせて、粘着剤組成物C6由来の厚さ20μmの電磁波剥離型粘着剤層、および、粘着剤組成物C2由来の厚さ25μmの粘着剤層を、形成した。このときの加熱温度は130℃であり且つ加熱時間は3分間である。以上のようにして、[電磁波剥離型粘着剤層/PET基材B2/粘着剤層(非電磁波剥離型)]の積層構造を有する実施例5の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその非電磁波剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの電磁波剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、実施例4に関して上述したのと同様にして、造形ステージ(紫外線透過性を有する)の表面の粘着シートに対してステージ側から紫外線照射を行い、当該粘着シートの電磁波剥離型粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。そして、電磁波照射に因って粘着力の低下した電磁波剥離型粘着剤層から造形物を引き離すことによって、造形ステージ上から造形物を取り外した。造形物が取り外された後、造形ステージ表面から粘着シートを剥離した。
〈伸張性基材の作製〉
ポリ塩化ビニル(商品名「TH-1300」,信越化学工業株式会社製)100質量部と、塩素化ポリエチレン(商品名「エラスレン302NA」,昭和電工株式会社製)10質量部と、アジピン酸系ポリエステル可塑剤(商品名「ポリサイザー W-2310」,DIC株式会社製)50質量部と、亜鉛石鹸としてのラウリン酸亜鉛(三津和化学薬品株式会社製)0.5質量部と、アルカリ土類金属石鹸としてのステアリン酸カルシウム(キシダ化学株式会社製)0.5質量部と、ハイドロタルサイト(商品名「アルカマイザー」,協和化学工業株式会社製)2質量部と、黒色顔料 2質量部とを混合して、ポリ塩化ビニル(PVC)組成物を調製した。このPVC組成物から、カレンダー成形機を使用してPVCフィルム(厚さ100μm)を作製した。このPVCフィルムの片面にて、上述の下塗り剤U2を塗布してこれを乾燥させ、下塗り層(約1g/m2)を形成した。以上のようにして、片面に下塗り層を有する伸張性基材を作製した。
スチレン-ブタジエンゴム(商品名「SBR1013」,結合スチレン量43質量%,JSR株式会社製)50質量部と、天然ゴム(商品名「RSS1級」,野村貿易株式会社製)50質量部と、テルペン樹脂(商品名「YSレジン PX1150」,軟化温度115℃,ヤスハラケミカル株式会社製)50質量部と、アルキルフェノール樹脂(商品名「タッキロール201」,田岡化学工業株式会社製)10質量部と、有機金属化合物アルミキレート(商品名「ALCH」,川研ファインケミカル株式会社製」7質量部と、フェノール系老化防止剤(商品名「イルガノックス1010」,BASF社製)1質量部と、溶媒としてのトルエンとを混合して、粘着剤層形成用の固形分濃度20質量%の組成物(粘着剤組成物C7)を作製した。次に、伸張性基材における、下塗り層が形成されている側の面にて、粘着剤組成物C7を塗布してこれを乾燥させ、厚さ10μmの粘着剤層を形成した。以上のようにして、[伸張性基材/ゴム系粘着剤層]の積層構造を有する実施例6の造形ステージ用の粘着シート(片面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの伸張性基材に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、粘着シートの端部を当該粘着シートの面広がり方向に引っ張ることによって粘着シートを延伸し、粘着剤層の造形ステージ表面に対する粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。その後、造形ステージ表面の粘着シートについて、粘着力の低下した粘着剤層を造形ステージ表面から離す剥離作業を行い、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈造形ステージ用粘着シートの作製〉
上述のアクリル系ポリマー溶液S2に、この溶液S2中の固形分(上述のアクリル系ポリマーA2)100質量部に対して5質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)と、20質量部の粘着付与剤(商品名「スミライトレジン PR12603」,住友デュレズ株式会社製)と、20質量部のロジンエステル(商品名「エステルガムAT」,荒川化学工業株式会社製)とを配合して、粘着剤層形成用の組成物(粘着剤組成物C8)を作製した。マニラ麻の不織布基材(厚さ50μm,坪量20g/m2)の両面にて、粘着剤組成物C8を塗布して乾燥させ、厚さ55μmの粘着剤層を形成した。以上のようにして、[粘着剤層/不織布基材/粘着剤層]の積層構造を有する粘着シートを作製した。一方、上述のアクリル系ポリマー溶液S2に、この溶液S2中の固形分(上述のアクリル系ポリマーA2)100質量部に対して5質量部のイソシアネート系架橋剤(商品名「コロネートL」,ポリイソシアネート化合物,東ソー株式会社製)と100質量部の熱膨張性微小球(商品名「マツモトマイクロスフェアー F-50D」,120℃膨張タイプ,松本油脂製薬株式会社製)とを配合して、熱剥離型粘着剤層形成用の組成物(粘着剤組成物C9)を作製した。次に、厚さ25μmのポリエステルフィルムの片面を剥離処理して得た剥離フィルムの剥離処理面に、粘着剤組成物C9を塗布して粘着剤組成物層を形成した。次に、剥離フィルム上で当該粘着剤組成物層について加熱によって乾燥させ且つ架橋反応を生じさせて、厚さ50μmの熱剥離型粘着剤層を形成した。このときの加熱温度は100℃であり且つ加熱時間は5分間である。そして、粘着剤組成物C8から形成された粘着剤層を両面に有する上記粘着シートの片面の粘着剤層と当該熱剥離型粘着剤層とを貼り合せた。以上のようにして、[粘着剤層(非熱剥離型)/不織布基材/粘着剤層(非熱剥離型)/熱剥離型粘着剤層]の積層構造を有する実施例7の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその熱剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの非熱剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージの造形物形成面を120℃に昇温させて当該表面の粘着シートの熱剥離型粘着剤層を加熱し、当該粘着剤層中の熱膨張性微小球を膨張させて当該粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。その後、造形ステージ表面の粘着シートについて、加熱に因って粘着力の低下した熱剥離型粘着剤層を造形ステージ表面から離す剥離作業を行い、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈造形ステージ用粘着シートの作製〉
上述のPET基材B1の一方の面(下塗り層が設けられていない側の面)に電磁波剥離型粘着剤層形成用の上述の粘着剤組成物C5を塗布して粘着剤組成物層を形成した。次に、当該粘着剤組成物層について加熱によって乾燥させ且つイソシアネート架橋剤による架橋反応を生じさせて、厚さ20μmの電磁波剥離型粘着剤層を形成した。このときの加熱温度は130℃であり且つ加熱時間は3分間である。一方、厚さ25μmのポリエステルフィルムの片面を剥離処理して得た剥離フィルムの剥離処理面に、熱剥離型粘着剤層形成用の上述の粘着剤組成物C9を塗布して粘着剤組成物層を形成した。次に、剥離フィルム上で当該粘着剤組成物層について加熱によって乾燥させ且つ架橋反応を生じさせて、厚さ50μmの熱剥離型粘着剤層を形成した。このときの加熱温度は100℃であり且つ加熱時間は5分間である。そして、粘着剤組成物C5から形成された電磁波剥離型粘着剤層を一方の面の側に伴う上記PET基材B1の他方の面(下塗り層側の面)の側に、当該熱剥離型粘着剤層を貼り合せた。以上のようにして、[電磁波剥離型粘着剤層/PET基材B1/熱剥離型粘着剤層]の積層構造を有する実施例8の造形ステージ用の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその熱剥離型粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの電磁波剥離型粘着剤層に強固に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージ(紫外線透過性を有する)の表面の粘着シートに対してステージ側から紫外線照射を行い、当該粘着シートの電磁波剥離型粘着剤層の粘着力を低下させた(これにより、造形ステージに対する造形物の、粘着シートを介した定着状態は、解除された)。この紫外線照射は、紫外線照射装置として高圧水銀灯を使用して、出力75Wによる照射強度150mW/cm2および紫外線照射積算光量500mJ/cm2の照射条件で行った。そして、電磁波照射に因って粘着力の低下した電磁波剥離型粘着剤層から造形物を引き離すことによって、造形ステージ上から造形物を取り外した。次に、造形ステージの造形物形成面を120℃に昇温させて当該表面の粘着シートの熱剥離型粘着剤層を加熱し、当該粘着剤層中の熱膨張性微小球を膨張させて当該粘着剤層の粘着力を低下させ、当該粘着シートを造形ステージ表面から剥がした。
〈粘着シートの作製〉
上述のアクリル系ポリマー溶液S8と、四官能エポキシ系架橋剤(商品名「TETRAD-C」,三菱瓦斯化学株式会社製)と、重合ロジンエステル(商品名「ペンセルD-135」,荒川化学工業株式会社製)とを、溶液S8が100質量部、四官能エポキシ系架橋剤が0.02質量部、および重合ロジンエステルが40質量部の量比で配合して、粘着剤層形成用の組成物(粘着剤組成物C11)を作製した。次に、表面に剥離処理の施された厚さ38μmのポリエステルフィルム(剥離フィルム)上に、粘着剤組成物C11を塗布して粘着剤組成物層を形成した。次に、剥離フィルム上で当該粘着剤組成物層について乾燥させ且つ架橋反応を生じさせて、厚さ65μmの粘着剤層を形成した。このときの加熱温度は100℃であり、加熱時間は3分間である。このような手法により、剥離フィルム付きの粘着剤層(厚さ65μm)を二つ形成した。次に、マニラ麻の不織布基材(厚さ50μm,坪量20g/m2)の両面のそれぞれに当該粘着剤層を貼り合せた。以上のようにして、[粘着剤層/不織布基材/粘着剤層]の積層構造を有する比較例1の粘着シート(両面粘着シート)を作製した。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその一方の粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの他方の粘着剤層に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージ表面の粘着シートについて、粘着剤層を造形ステージ表面から離す剥離作業を試み、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
〈粘着シートの作製〉
不織布基材の代わりに上記のPET基材B1を用いたこと、および、粘着剤組成物C11から厚さ65μmの粘着剤層の代わりに厚さ30μmの粘着剤層を形成したこと以外は比較例1と同様にして、比較例2の粘着シート(両面粘着シート)を作製した。比較例2の粘着シートは、[粘着剤層/PET基材B1/粘着剤層]の積層構造を有する。
以上のようにして作製された粘着シートを、当該粘着シートにシワも部分的な浮きも生じさせずにその一方の粘着剤層を介して3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。そして、実施例1に関して上述したのと同様の条件で3Dプリンタを稼動させて、造形ステージ上に平板形状の造形物(100mm×100mm,厚さ2mm)を形成した。造形物は、造形ステージ表面の粘着シートの他方の粘着剤層に定着した状態で、形成された。造形物形成過程を終えて造形物を放冷した後、造形ステージ表面の粘着シートについて、粘着剤層を造形ステージ表面から離す剥離作業を試み、これに伴って造形ステージ上から造形物を取り外した。そして、当該造形物から粘着シートを剥がした。
実施例1~8および比較例1,2の各粘着シートについて、3Dプリンタを稼働して平板形状の造形物を造形する上記造形物形成過程の終了後の、造形ステージ上からの造形物の取り外しやすさを調べた。実施例1~3,6,7の各粘着シートについては、上述のように、粘着シートに対応した粘着力低下措置を経た後に、造形ステージからの当該粘着シートの剥離作業に伴って造形物を造形ステージ上から取り外した。実施例4,5,8の各粘着シートについては、上述のように、粘着シートに対応した粘着力低下措置を経た後に、表面に粘着シートを伴う造形ステージ上から造形物を取り外した。比較例1,2の各粘着シートについては、上述のように、造形ステージからの当該粘着シートの剥離作業を試みることによって造形物を造形ステージ上から取り外した。造形ステージ上からの造形物の取り外しに関し、容易に造形物を取り外すことができる場合を非常に取り外しやすい(◎)と評価し、取り外すためには、非常に取り外しやすい場合よりも有意に大きな力を要する場合を取り外しにくい(△)と評価し、鋭利な先端を有するスクレーパー等の道具を使用せずには取り外しが困難である場合を取り外し困難(×)と評価した。その結果を表1~3に掲げる。
実施例6の粘着シートについて、造形ステージ上からの造形物の取り外しに要する剥離力、即ち、造形物を伴いつつ造形ステージ表面から粘着シートを剥離するために要する外力を測定した。具体的には、まず、粘着シートを、積層造形装置たる熱溶解積層方式3Dプリンタ(商品名「BS01+」,ボンサイラボ株式会社製)の造形ステージの造形物形成面に貼り合わせた。貼合せにおいては、粘着シートにシワも造形ステージからの部分的な浮きも生じさせずに、当該粘着シートの熱剥離型粘着剤層側を造形物形成面に貼着させた。次に、3Dプリンタを稼動させて造形物を形成した。具体的には、3Dプリンタの備えるモデル材吐出用ノズルから造形ステージに向けて、ノズル内部で240℃に加熱されたモデル材たるABS樹脂フィラメント(商品名「プラシル」,断面直径1.75mm,ホワイトカラータイプ,プラシル社製)を吐出供給して、表面に造形ステージ用の粘着シートを伴う造形ステージの上に造形物を形成した。造形物形成過程中の造形ステージの造形物形成面の温度は100℃とした。形成した造形物は、図21に示すような本体部201および壁部202を有する。本体部201は、平面視矩形の平板形状(100mm×100mm,厚さ2mm)を有する。壁部202は、本体部201の縁端に位置して本体部201の一辺の全体に沿って延び、7mmの高さ及び2mmの厚さを有する。また、壁部202は、直径2mmの孔(図示略)を伴う形状で形成された部位である。この孔は、壁部202の延び方向における中央に位置し、且つ、壁部202を厚さ方向に貫通する。次に、造形物形成過程終了の後に造形ステージが30℃まで降温したところで、粘着シートの端部を当該粘着シートの面広がり方向に4.5kg重の力で引っ張ることによって粘着シートを延伸し、その粘着剤層の造形ステージ表面に対する粘着力を低下させた。そして、造形物の壁部202にその孔を利用して一端を結び付けたストリングを図21中の矢印Dで示す方向に引っ張ることによって造形ステージ上から造形物を取り外すのに要する外力(最大値)を、剥離力として、当該ストリングの他端が結び付けられたプッシュプルゲージ(商品名「PS(Max. Capacity 5kg)」,株式会社今田製作所製)を使用して測定した。本測定における測定値は0kg重であった。すなわち、取り外し対象の造形物は、実質的には、粘着シートの上述の延伸によって造形ステージ上から既に取り外された状態にあった。
本発明の構成を具備する実施例1~8の造形ステージ用粘着シートによると、表1,2における“造形後の造形物の取り外し”の項目に評価結果を示すとおり、造形物形成過程終了後に造形ステージ上から造形物を容易に取り外すことが可能である。上述の測定方法によって測定される、造形物の取り外しに要する力は、実施例6の粘着シートでは0kg重であり、実施例7の粘着シートでは0.05kg重であり、共に非常に小さい。これに対し、比較例1,2の粘着シートによると、表3における“造形後の造形物の取り外し”の項目に評価結果を示すとおり、造形物形成過程終了後に造形ステージ上から造形物を容易に取り外すことはできなかった。上述の測定方法によって測定される、造形物の取り外しに要する力は、比較例1の粘着シートでは測定限界以上、即ち5kg重以上であった。
S1,S2,S3 基材
11,12,21,22,31,32,41,42,51,52,61,62 粘着剤層
100 造形ステージ
101 造形物形成面
110 加熱ユニット
120 冷却ユニット
130 電磁波照射ユニット(電磁波照射手段,粘着力低下手段)
140 電圧印加ユニット(電圧印加手段,粘着力低下手段)
150 液体供給ユニット
160 延伸ユニット
170 磁場印加ユニット
Claims (25)
- 粘着力低下措置に因って粘着力が低下可能な、粘着剤を含む粘着剤層、を有する造形ステージ用粘着シート。
- 前記粘着剤層は熱剥離型粘着剤層であり、前記粘着力低下措置は当該粘着剤層の加熱である、請求項1に記載の造形ステージ用粘着シート。
- 前記熱剥離型粘着剤層は熱膨張剤を含む、請求項2に記載の造形ステージ用粘着シート。
- 前記熱膨張剤は、加熱によってガス化する成分と、当該成分を封入して当該成分のガス化によって膨張および/または破断を生じ得る殻とを備える、熱膨張性微小球である、請求項3に記載の造形ステージ用粘着シート。
- 前記粘着剤層は冷却剥離型粘着剤層であり、前記粘着力低下措置は当該粘着剤層の冷却である、請求項1に記載の造形ステージ用粘着シート。
- 前記冷却剥離型粘着剤層は側鎖結晶性ポリマーを含む、請求項5に記載の造形ステージ用粘着シート。
- 前記粘着剤層は電磁波剥離型粘着剤層であり、前記粘着力低下措置は当該粘着剤層に対する電磁波照射である、請求項1に記載の造形ステージ用粘着シート。
- 前記電磁波剥離型粘着剤層は電磁波硬化性成分を含む、請求項7に記載の造形ステージ用粘着シート。
- 前記粘着剤層は電気剥離型粘着剤層であり、前記粘着力低下措置は当該粘着剤層に対する電圧印加である、請求項1に記載の造形ステージ用粘着シート。
- 前記電気剥離型粘着剤層は電解質を含む、請求項9に記載の造形ステージ用粘着シート。
- 前記電解質はイオン液体である、請求項10に記載の造形ステージ用粘着シート。
- 前記電気剥離型粘着剤層における前記電解質の含有量は、前記粘着剤100質量部に対して0.5~30質量部である、請求項10または11に記載の造形ステージ用粘着シート。
- 前記粘着剤層は液体剥離型粘着剤層であり、前記粘着力低下措置は当該粘着剤層への液体供給である、請求項1に記載の造形ステージ用粘着シート。
- 前記液体剥離型粘着剤層は水溶性粘着剤を含む、請求項13に記載の造形ステージ用粘着シート。
- 伸張性基材と前記粘着剤層とを含む積層構造を有し、前記粘着力低下措置は当該造形ステージ用粘着シートの延伸である、請求項1に記載の造形ステージ用粘着シート。
- 破断時伸び(JIS K 7311-1995)が300%以上である、請求項15に記載の造形ステージ用粘着シート。
- 前記粘着剤はアクリル系粘着剤を含む、請求項1から16のいずれか一つに記載の造形ステージ用粘着シート。
- 前記粘着剤層の厚さ1~1000nmである、請求項1から17のいずれか一つに記載の造形ステージ用粘着シート。
- 請求項1に記載の造形ステージ用粘着シートを使用することが可能な積層造形装置であって、
造形ステージと、
前記造形ステージ上に貼り合わされた前記造形ステージ用粘着シートの前記粘着剤層に対して前記粘着力低下措置を行うための粘着力低下手段とを備える、積層造形装置。 - 前記粘着剤層は電磁波剥離型粘着剤層であり、前記粘着力低下手段は、当該粘着剤層に対して電磁波照射を行うための電磁波照射手段である、請求項19に記載の積層造形装置。
- 前記電磁波剥離型粘着剤層は電磁波硬化性成分を含む、請求項20に記載の積層造形装置。
- 前記粘着剤層は電気剥離型粘着剤層であり、前記粘着力低下手段は、当該粘着剤層に対して電圧印加を行うための電圧印加手段である、請求項19に記載の積層造形装置。
- 前記電気剥離型粘着剤層は電解質を含む、請求項22に記載の積層造形装置。
- 前記電解質はイオン液体である、請求項23に記載の積層造形装置。
- 前記電気剥離型粘着剤層における前記電解質の含有量は、前記粘着剤100質量部に対して0.5~30質量部である、請求項23または24に記載の積層造形装置。
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JP2022500278A (ja) * | 2018-09-11 | 2022-01-04 | メルド マニュファクチュアリング コーポレイション | 導電性ポリマー複合材料を合成するための固体添加物製造方法、導電性プラスチックパーツ及び導電性コーティングの製造 |
JP7451500B2 (ja) | 2018-09-11 | 2024-03-18 | メルド マニュファクチュアリング コーポレイション | 導電性ポリマー複合材料を合成するための固体添加物製造方法、導電性プラスチックパーツ及び導電性コーティングの製造 |
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WO2022025722A1 (ko) * | 2020-07-30 | 2022-02-03 | 박희용 | 3차원 프린터를 이용한 입체간판 제작방법 |
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Also Published As
Publication number | Publication date |
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CN109070470A (zh) | 2018-12-21 |
JPWO2017187800A1 (ja) | 2019-02-28 |
JP6824254B2 (ja) | 2021-02-03 |
US20210179893A1 (en) | 2021-06-17 |
EP3450143A1 (en) | 2019-03-06 |
EP3450143A4 (en) | 2019-12-25 |
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