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WO2013129096A1 - Composition adhésive hydrophile durcissable par rayons d'énergie, feuille adhésive et structure hydrophile - Google Patents

Composition adhésive hydrophile durcissable par rayons d'énergie, feuille adhésive et structure hydrophile Download PDF

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Publication number
WO2013129096A1
WO2013129096A1 PCT/JP2013/053280 JP2013053280W WO2013129096A1 WO 2013129096 A1 WO2013129096 A1 WO 2013129096A1 JP 2013053280 W JP2013053280 W JP 2013053280W WO 2013129096 A1 WO2013129096 A1 WO 2013129096A1
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Prior art keywords
sensitive adhesive
pressure
adhesive composition
energy ray
curable
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Ceased
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English (en)
Japanese (ja)
Inventor
和恵 上村
海佐 ▲柳▼本
有美 平手
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Lintec Corp
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Lintec Corp
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Priority to JP2014502115A priority Critical patent/JP6086899B2/ja
Publication of WO2013129096A1 publication Critical patent/WO2013129096A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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 an energy beam curable hydrophilic pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet, and more specifically, an energy beam curable hydrophilic pressure-sensitive adhesive composition suitable for three-dimensional stretching that is three-dimensionally stretched and a structure composed thereof.
  • the present invention relates to a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer and a hydrophilic structure obtained from the pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer.
  • a module is called a ⁇ TAS (Micro Total Analysis System) or a microreactor.
  • This microreactor has the advantage that the efficiency of heating and cooling is high because the amount of the target substance to be analyzed or synthesized is small, and the reaction speed is high because the diffusion length of the target substance is short. Further, since the entire system is miniaturized, there is an advantage that time required for analysis is shortened and rapid evaluation is possible. Furthermore, even when it is necessary to discard the equipment used for analysis or reaction, there is an advantage that the total cost required for disposal can be suppressed because the entire used module may be discarded.
  • Patent Document 1 has three or more merging units composed of two or more inflow passages, a merging portion where they merge, and one outflow passage extending in the downstream direction from the merging portion.
  • the minute merge channel structure one merge unit is disposed on the most downstream side, and its outflow path is an outlet of the minute merge channel structure, and the remaining merge unit outflow paths are located further downstream.
  • a minute merge channel structure characterized in that it is an inflow channel of a merge unit, and the remaining inflow channel is an inlet of the minute merge channel structure.
  • Patent Document 2 discloses a plurality of reaction vessels arranged on the same plane, and each reaction vessel connected to each reaction vessel through a fine channel, and a reaction solution provided on the plane on which the plurality of reaction vessels are arranged.
  • a biological sample reaction chip is disclosed that includes an introduction channel and a reaction solution movement stop unit that is connected to a terminal portion of the reaction solution introduction channel and that can control the movement of the reaction solution.
  • Patent Document 3 discloses a micro flow channel for supplying a liquid to a sensor or discharging a liquid supplied to the sensor, and the flow channel body used in an upright state has a divided surface parallel to the flow channel center line.
  • the first wall surface portion that exhibits hydrophobicity and the second wall surface portion that exhibits hydrophilicity are divided, and the flow path body has a condition represented by a specific expression using the shape of the flow path as a parameter.
  • a microchannel characterized by filling is disclosed.
  • the structure of such a microreactor is premised on the application of the microfabrication technology that has been used in the manufacture of semiconductor devices.
  • a semiconductor material such as silicon or an inorganic material such as glass is used as the material.
  • the material of the microreactor disclosed in Patent Document 2 is glass.
  • the microreactor disclosed in Patent Document 3 is made of plastic and glass.
  • a resin material contains a resin component as one of the main components, and can enjoy the advantages of the resin material as a whole (especially the high ability to create shapes described later) to the same extent as the resin material.
  • Patent Document 4 as a material for forming a structure formed by molding a two-dimensional or three-dimensional microchannel or nanochannel on the surface, the first component is a polypropylene resin, A synthetic resin composition comprising two or more synthetic resin components in which two components are hydrogenated derivatives of a block copolymer represented by the general formula XY is disclosed.
  • Patent Document 5 discloses a resin-filler composite material for a resin substrate for a microreactor, wherein the filler has an inorganic material or a polymer material having an aspect ratio of 10 or more, or a birefringence index of a predetermined value or more.
  • a material that contains 0.01 to 200 parts by weight of a filler per 100 parts by weight of a resin is disclosed.
  • resin-based materials as microreactor materials have over other materials (semiconductors such as silicon, inorganic materials such as glass, and metals) is compared to other materials. Therefore, shape creation is easy and the degree of freedom of shapes that can be created may be high. For example, if injection molding technology, blow molding technology or press molding technology is applied using a thermoplastic resin as a resin-based material, a concave shape with a high aspect ratio or a complicated step shape is generally used in the manufacture of semiconductor devices. Compared with the case of using the microfabrication technique used, it is possible to manufacture easily.
  • the resin-based material has a problem that its surface is generally hydrophobic. Considering that in many cases the liquid flowing in the microreactor is an aqueous solution (almost all are aqueous solutions in the case of bio-related applications), the hydrophobicity of the microreactor disclosed in Patent Document 3 is positive. Unless there is a circumstance where the microreactor is used, at least the liquid contact surface is required to be hydrophilic.
  • Another example of means for hydrophilizing the liquid contact surface of a microreactor made of a resin material is to include a hydrophilicity imparting agent in the resin material.
  • the most common such materials are surfactants and ionic liquids.
  • resin-based materials containing surfactants and ionic liquids essentially avoid the elution of ionic substances from the resin-based materials because the ionic substances physically move within the resin-based materials. I can't. Although measures can be taken to reduce the extent of elution, the fact of elution reduces the reliability of the analysis results and raises concerns about the impact on the organism in bio-related applications. Therefore, it is practically unacceptable to apply a means for changing the physical properties of the resin material using a surfactant or an ionic liquid to the microreactor.
  • the present invention includes a resin material suitable as a constituent material of a microstructure having a hydrophilic surface represented by a microreactor, specifically, a resin composition and a layer made of the resin composition. It is an object to provide a sheet.
  • the present invention provided in order to solve the above-mentioned problems is, firstly, energy beam curing containing an energy beam curable resin and a particulate hydrophilicity imparting agent dispersed in the energy beam curable resin.
  • Type hydrophilic pressure-sensitive adhesive composition wherein the energy ray-curable hydrophilic pressure-sensitive adhesive composition has a breaking elongation of 2000% or more and a stress relaxation rate of 70% or more and 95% or less before energy ray curing.
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition is used as a 20 ⁇ m-thick pressure-sensitive adhesive layer formed on a 38 ⁇ m-thick polyethylene terephthalate resin sheet, and the pressure-sensitive adhesive layer is energy-ray-cured to form a pressure-sensitive adhesive cured layer.
  • the half-life of the charged voltage measured using a half-life measuring instrument defined in JIS L1094: 1997 is 60 seconds or less at 25 ° C. and 50% RH.
  • An energy ray-curable hydrophilic pressure-sensitive adhesive composition (Invention 1) is provided.
  • hydrophilicity in the energy ray-curable hydrophilic pressure-sensitive adhesive composition means that the surface of the cured product obtained by energy ray-curing the pressure-sensitive adhesive composition has hydrophilicity.
  • the hydrophilicity-imparting agent is in the form of particles, the hydrophilicity-imparting agent is detached from the structure in use, and the hydrophilicity of the surface of the structure is lowered, or a substance that is in contact with the structure (for example, a reaction solution) ) Is suppressed.
  • the energy ray curable resin has a sufficiently high breaking elongation before curing, three-dimensional structures having various shapes can be obtained. By curing this three-dimensional structure with energy rays, a hydrophilic structure that can be suitably used as a microreactor or the like can be obtained.
  • an average particle size of the particulate hydrophilicity-imparting agent is 1000 nm or less (Invention 2).
  • the average particle size is 1000 nm or less, the surface roughness of the hydrophilic three-dimensional structure obtained by energy ray curing is reduced, and excellent surface properties are easily obtained.
  • the particulate hydrophilicity-imparting agent is preferably made of a metal oxide (Invention 3). Since the particulate hydrophilicity imparting agent made of a metal oxide is excellent in optical properties, the possibility of occurrence of curing variation when the energy ray-curable hydrophilic pressure-sensitive adhesive composition is cured is reduced. Moreover, it becomes easy to observe the content (for example, reaction liquid) of the hydrophilic three-dimensional structure obtained by energy ray curing.
  • the metal oxide may contain one or more selected from the group consisting of phosphoric acid-doped tin oxide and a double oxide consisting of zinc oxide and antimony pentoxide. Preferred (Invention 4). These metal oxides are particularly excellent in optical properties.
  • the total light transmittance before energy ray curing when the energy ray curable hydrophilic adhesive composition is a 5 ⁇ m thick adhesive layer is 80% or more, and It is preferable that the adhesive layer has a haze of 10% or less (Invention 5).
  • the possibility of variation in curing in the composition is particularly reduced, and it becomes easy to observe the contents of the cured hydrophilic three-dimensional structure. .
  • the energy ray curable resin preferably contains a (meth) acrylic acid ester copolymer and an energy ray curable urethane acrylate (Invention 6).
  • a (meth) acrylic acid ester copolymer and an energy ray curable urethane acrylate (Invention 6).
  • the content of the energy ray curable urethane acrylate is preferably 50 to 200 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer (Invention 7). ).
  • the above composition can be sufficiently cured, and it becomes easy to maintain the shape when the composition is formed into a sheet shape or the like.
  • the glass transition temperature (Tg) before energy ray curing of the (meth) acrylic acid ester copolymer is ⁇ 50 to 0 ° C.
  • the energy ray curable urethane acrylate is preferably ⁇ 40 to 20 ° C. (Invention 8).
  • the pencil hardness after energy ray curing of the energy ray curable urethane acrylate is preferably B to 5B (Invention 9).
  • the energy ray curable hydrophilic pressure-sensitive adhesive composition of the above invention (Invention 1 to 9) is preferably used for three-dimensional molding (Invention 10).
  • the energy beam curable hydrophilic pressure-sensitive adhesive composition according to the present invention is excellent in curability and mechanical properties before and after curing. Therefore, it is suitable as a material for performing three-dimensional molding.
  • the energy ray curable hydrophilic pressure-sensitive adhesive composition may be three-dimensionally molded by three-dimensionally extending (invention 11). Even if this composition is three-dimensionally stretched, it has excellent elongation at break before curing, so the composition is less likely to cohesively break in the process, and the stress relaxation rate before curing is within an appropriate range, so The shape is difficult to change in between.
  • the present invention secondly provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer composed of the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to any one of the above inventions (Inventions 1 to 11). (Invention 12)
  • This pressure-sensitive adhesive sheet is easy to maintain its shape because the composition according to any of the above inventions (inventions 1 to 11) is excellent in mechanical properties before being cured. When molded, problems such as cohesive failure are unlikely to occur. Furthermore, since this adhesive sheet has hydrophilicity, a hydrophilic three-dimensional structure can be obtained.
  • the present invention provides a pressure-sensitive adhesive layer composed of the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to any one of the above inventions (Inventions 1 to 11), and two sheets sandwiching the pressure-sensitive adhesive layer.
  • a pressure-sensitive adhesive sheet comprising a release sheet is provided (Invention 13).
  • this pressure-sensitive adhesive sheet can appropriately protect the pressure-sensitive adhesive layer composed of the composition according to any of the above inventions (inventions 1 to 11) until it is attached to the adherend, Possibility that the adhesiveness of the surface which makes the bonding surface falls or the surface is contaminated is reduced.
  • the present invention is that the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to any one of the above inventions (Inventions 1 to 11) is three-dimensionally molded by three-dimensionally extending. A hydrophilic structure is provided (Invention 14).
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to any one of the above inventions (Inventions 1 to 11) has excellent mechanical properties, various hydrophilic structures obtained by three-dimensional molding of such a composition are available. Can have various shapes.
  • the present invention fifthly is characterized in that the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to any of the above inventions (Inventions 12 and 13) is three-dimensionally molded by three-dimensionally extending. A hydrophilic structure is provided (Invention 15).
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet according to any of the above inventions has excellent mechanical properties, the composition is three-dimensionally molded. The resulting hydrophilic structure can have various shapes.
  • the energy ray curable hydrophilic pressure-sensitive adhesive composition of the present invention has a particulate hydrophilicity imparting agent, and the surface of a structure (for example, a microreactor) obtained from the composition is made hydrophilic by the particulate hydrophilicity imparting agent. Turn into.
  • a particulate hydrophilicity-imparting agent By using such a particulate hydrophilicity-imparting agent, the hydrophilicity-imparting agent is detached from the structure in use, the hydrophilicity of the surface of the structure is reduced, or a substance (for example, a reaction solution) that comes into contact with the structure ) Is suppressed.
  • a hydrophilic structure having high mechanical strength can be obtained by energy beam curing of the three-dimensional structure thus obtained, and such a structure can be suitably used as a microreactor or the like.
  • FIG. 10 is a cross-sectional view conceptually showing a cross-sectional view of an ion elution test cell for performing an ion elution test in Test Example 8.
  • three-dimensional molding means a shape creation processing method that forms a predetermined shape by three-dimensionally extending a material to be processed, and the term “extension” includes the concept of expansion. Shall be included.
  • the breaking elongation of the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to this embodiment is 2000% or more.
  • the elongation at break was measured by processing the hydrophilic pressure-sensitive adhesive composition into a single pressure-sensitive adhesive layer without a substrate or the like. Specifically, the thickness was 500 ⁇ m, the width was 15 mm, and the length was 55 mm. 25 mm), the hydrophilic pressure-sensitive adhesive composition is stretched at a speed of 200 mm / min in an environment of 23 ° C. and 50% RH.
  • the stress relaxation rate of the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to this embodiment is 70 to 95%, preferably 75 to 93%, and particularly preferably 80 to 91%.
  • the stress relaxation rate is 70% or more, the hydrophilic pressure-sensitive adhesive composition can be easily held in a stretched state, so that it can be easily molded into a target shape.
  • the stress relaxation rate is 95% or less, the shape is further deformed by an external force (for example, gravity, etc.) other than the force for extending the hydrophilic pressure-sensitive adhesive composition while maintaining the fully extended state. Can be suppressed.
  • the stress relaxation rate refers to the ratio of the stress obtained by stretching the hydrophilic pressure-sensitive adhesive composition by 300% in the tensile test to the stress at the time of holding for 300 seconds.
  • the tensile conditions were as follows: a hydrophilic pressure-sensitive adhesive composition molded into a thickness of 500 ⁇ m, a width of 15 mm, and a length of 55 mm (of which the measurement range was 25 mm), in an environment of 23 ° C. and 50% RH, It shall be performed by stretching 300% at a speed of 200 mm / min.
  • the surface of the cured product obtained by energy beam curing from the energy-beam curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment has hydrophilicity.
  • a 20 ⁇ m thick adhesive layer is formed on a 38 ⁇ m thick polyethylene terephthalate resin sheet, and the adhesive cured layer obtained by energy ray curing of this adhesive layer is a half-life defined in JIS L1094: 1997.
  • the half-life of the charged voltage measured using a measuring instrument (the time until the charged voltage is attenuated to 1/2 at 25 ° C. and 50% RH after being charged by corona discharge) is 60 seconds or less.
  • the surface of the pressure-sensitive adhesive cured layer has sufficient hydrophilicity, and the occurrence of problems due to insufficient hydrophilicity can be suppressed.
  • a specific example of the above problem is that the liquid does not enter the concave portion of the microstructure, and at this time, the reaction that is scheduled to proceed in the concave portion does not proceed, and the liquid is in the concave portion that is the measurement unit. There may be a problem that it does not exist and cannot be analyzed.
  • Another example of the above problem is that turbulent flow occurs in the flow path and entrainment of bubbles occurs. At this time, the flow rate management related to the reaction is insufficient, and the reaction does not proceed as planned. There may be a problem that the reliability of the measurement result is lowered due to the addition of bubble information during measurement.
  • the surface of the pressure-sensitive adhesive cured layer has particularly excellent hydrophilicity, and it is possible to more stably avoid the above problems.
  • the hydrophilic adhesive composition As a hydrophilicity evaluation method, it is common to measure the contact angle of a droplet formed on a flat resin material to be evaluated, but the hydrophilic adhesive composition according to this embodiment Since the product contains a particulate hydrophilicity imparting agent, the surface of the pressure-sensitive adhesive cured layer may have irregularities depending on the shape (particle size, etc.) of the particulate hydrophilicity imparting agent. In this case, since the interface between the droplet and the resin-based material does not form a flat surface, the reliability is low even if the contact angle of the droplet is measured.
  • the contact angle as a criterion for determining whether or not the surface of the pressure-sensitive adhesive cured layer has sufficient hydrophilicity.
  • the measurement result is hardly influenced by the surface property of the pressure-sensitive adhesive cured layer, it is possible to stably and quantitatively evaluate the degree of hydrophilicity.
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment has a total light transmittance as defined in JIS K7361-1: 1997 of a layer having a thickness of 5 ⁇ m of 80% or more before energy ray curing. It is preferable that Moreover, it is preferable that the above-mentioned pressure-sensitive adhesive layer has a haze defined in JIS K7136: 2000 of 10% or less before energy ray curing. In the case of providing these optical characteristics, even when the structure is made into a three-dimensional shape by three-dimensional molding, it is stably realized that the energy rays irradiated to the entire structure reach. Therefore, by having these optical properties, local deterioration of the mechanical properties in the structure after curing is stably avoided.
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition comprises an energy ray-curable resin and a hydrophilic pressure-sensitive adhesive composition containing a particulate hydrophilicity imparting agent dispersed in the energy ray-curable resin. It is a thing. Hereinafter, the composition of the energy beam curable resin and the particulate hydrophilicity imparting agent will be described in detail.
  • the composition of the energy beam curable resin according to the present embodiment is arbitrary as long as the energy beam curable hydrophilic pressure-sensitive adhesive composition before curing satisfies the mechanical properties (breaking elongation and stress relaxation rate).
  • the energy beam curable resin according to the present embodiment preferably contains (1) a (meth) acrylic acid ester copolymer and (2) an energy beam curable urethane acrylate, and (3) a photopolymerization initiator. Those further containing are particularly preferred.
  • the energy beam curable resin according to this embodiment may contain (4) other components, for example, a crosslinking agent.
  • (Meth) acrylic acid ester copolymer is not particularly limited, and (meth) acrylic acid ester copolymer conventionally used as a resin component of an acrylic pressure-sensitive adhesive composition. Any polymer can be appropriately selected and used.
  • a (meth) acrylic acid ester copolymer for example, a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 20 carbon atoms, a monomer having a functional group having active hydrogen, and, if desired, Preferred examples include copolymers with other monomers used.
  • (meth) acrylic acid ester means both acrylic acid ester and methacrylic acid ester. The same applies to other similar terms.
  • Examples of (meth) acrylic acid alkyl esters having an alkyl group with 1 to 20 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) Acrylate, octyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) Examples include acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like. These may
  • examples of monomers having a functional group having active hydrogen include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl Monoalkylaminoalkyl (meth) acrylates such as (meth) acrylate and monoethylaminopropyl (meth) acrylate; Ethyl such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid Such emissions unsaturated carboxylic acid. These monomers may be used independently and may be
  • Examples of other monomers used as desired include vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogenated olefins such as vinyl chloride and vinylidene chloride; Styrene monomers such as styrene and ⁇ -methylstyrene; Diene monomers such as butadiene, isoprene and chloroprene; Nitrile monomers such as acrylonitrile and methacrylonitrile; Acrylamide, N-methylacrylamide, N, N -Acrylamides such as dimethylacrylamide. These may be used alone or in combination of two or more.
  • (meth) acrylic acid ester copolymers those having an energy ray polymerizable group in the molecule (so-called adduct polymers) are particularly preferable.
  • adduct polymers those having an energy ray polymerizable group in the molecule
  • numerator of a (meth) acrylic acid ester copolymer for example, the (meth) acrylic acid ester copolymer (a1 which has a functional group containing monomer unit) ) And an unsaturated group-containing compound (a2) having a substituent that reacts with the functional group.
  • hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate are preferable.
  • a compound having a functional group that reacts with the hydroxy group of the component (a1) and a polymerizable double bond is preferable.
  • the amount of energy ray curable urethane acrylate that is a low molecular weight component can be reduced. It can suppress that the said low molecular weight component from a thing bleeds out. When bleeding out is suppressed, the composition of the hydrophilic pressure-sensitive adhesive composition does not change, so that the adhesive strength does not deteriorate with time as designed. At this time, in the extension molding described later, the hydrophilic pressure-sensitive adhesive composition Separation from the base can be suppressed. Therefore, it is preferable to use a (meth) acrylic acid ester copolymer having an energy ray polymerizable group in the molecule as the component (a2).
  • the copolymerization form of the (meth) acrylic acid ester copolymer is not particularly limited, and any of a random copolymer, a block copolymer, and a graft copolymer may be used.
  • the molecular weight of the (meth) acrylic acid ester copolymer is preferably 300,000 or more in terms of weight average molecular weight, and more preferably 350,000 to 2.5 million. If the weight average molecular weight is less than 300,000, the adhesion to the adherend and the durable adhesion may be insufficient. Considering adhesiveness and durable adhesiveness, the weight average molecular weight of the (meth) acrylic acid ester copolymer is preferably 400,000 to 1,800,000. In addition, the weight average molecular weight in this specification is the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method.
  • GPC gel permeation chromatography
  • the glass transition temperature (Tg) of the (meth) acrylic acid ester copolymer before curing with energy rays is preferably ⁇ 50 to 0 ° C., and particularly preferably ⁇ 40 to 0 ° C.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) of the (meth) acrylic acid ester copolymer is in this range, an appropriate balance between adhesive strength and breaking elongation can be achieved. Therefore, when a structure is obtained by creating a shape by elongation molding described later, the glass transition temperature (Tg) before energy ray curing of the (meth) acrylate copolymer can be set as described above. preferable.
  • Energy ray curable urethane acrylate is an oligomeric compound having a (meth) acryloyl group and a urethane bond. Since it has a (meth) acryloyl group in the molecule, it is polymerized by energy ray irradiation. It hardens
  • the energy ray curable urethane acrylate is obtained, for example, by reacting a polyisocyanate compound, a (meth) acrylate having a hydroxyl group or an isocyanate group, and a polyol compound.
  • the energy ray curable urethane acrylate include urethane obtained by further reacting a hydroxyl group-containing (meth) acrylate with a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyol compound and a polyisocyanate compound.
  • Examples thereof include urethane acrylates obtained by further reacting an isocyanate group-containing (meth) acrylate with an acrylate or a terminal hydroxyl group-containing urethane prepolymer obtained by reacting a polyol compound and a polyisocyanate compound.
  • polyisocyanate compound examples include isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′- And diisocyanates such as diisocyanate.
  • Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and polyethylene. Examples include glycol (meth) acrylate. Examples of the (meth) acrylate having an isocyanate group include methacryloyloxyethyl isocyanate.
  • polyol compound examples include polyol compounds such as alkylene type, polycarbonate type, polyester type, and polyether type. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycarbonate diol, polyester diol, And ether diol.
  • the above energy ray curable urethane acrylate may be used alone or in combination of two or more.
  • the weight average molecular weight of the energy ray curable urethane acrylate is preferably 1,000 to 12,000, particularly preferably 2,500 to 10,000, and more preferably 4,000 to 8,000. It is preferable.
  • the weight average molecular weight is 1,000 or more, a sufficient elongation at break can be obtained with the obtained hydrophilic pressure-sensitive adhesive composition, and when it is 12,000 or less, the hydrophilic pressure-sensitive adhesive composition is formed into a sheet ( When forming a pressure-sensitive adhesive layer comprising a hydrophilic pressure-sensitive adhesive composition), an optimum viscosity is expressed.
  • the glass transition temperature (Tg) after energy beam curing of the energy beam curable urethane acrylate is preferably ⁇ 40 to 20 ° C., particularly preferably ⁇ 20 to 10 ° C.
  • Tg glass transition temperature of the energy ray curable urethane acrylate
  • an appropriate balance between the adhesive strength and the elongation at break can be achieved. Therefore, when obtaining a structure by creating a shape by elongation molding described later, it is preferable to set the glass transition temperature (Tg) after energy beam curing of the energy beam curable urethane acrylate as described above.
  • the glass transition temperature (Tg) of the energy ray curable urethane acrylate is a value after energy ray curing, and this is a difference after irradiation with ultraviolet rays (illuminance 80 mW / cm, integrated light amount 800 mJ / cm 2 ). It is a value measured by scanning calorimetry (DSC method).
  • the pencil hardness after energy beam curing of the energy beam curable urethane acrylate is preferably B to 5B, particularly preferably 3B to 5B, more preferably 4B to 5B, and 5B. Is most preferred.
  • the pencil hardness is set to be equal to or higher than 5B, the hydrophilic pressure-sensitive adhesive composition has sufficient hardness after curing, so that the shape can be maintained well.
  • the pencil hardness is softer than 5B, the shape cannot be maintained, and there is a possibility that the three-dimensional molding cannot be performed.
  • the cured hydrophilic pressure-sensitive adhesive composition does not become brittle, so that brittle fracture of the structure made of the hydrophilic pressure-sensitive adhesive composition is suppressed. Can do.
  • the work of separating the cured hydrophilic pressure-sensitive adhesive composition from the base is performed. The structure is preferably prevented from being destroyed during this operation.
  • the energy ray curable urethane acrylate content (based on solid content) in the energy ray curable resin according to the present embodiment is 50 to 200 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer.
  • the amount is preferably 70 to 180 parts by mass, and more preferably 80 to 150 parts by mass.
  • the content of the energy ray curable urethane acrylate is 50 parts by mass or more, sufficient curability is obtained with the obtained hydrophilic pressure-sensitive adhesive composition, and when it is 200 parts by mass or less, it is a high molecular weight component ( The content of the (meth) acrylic acid ester copolymer can be sufficiently secured, and the shape can be maintained when the hydrophilic pressure-sensitive adhesive composition is stored in a sheet state.
  • the energy beam curable resin according to the present embodiment contains a photopolymerization initiator, so that the irradiation amount and irradiation time of the energy beam necessary for the polymerization and curing of the energy beam curable urethane acrylate are reduced. Can be reduced.
  • the photopolymerization initiator is not particularly limited.
  • These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the content (based on solid content) of the photopolymerization initiator in the energy beam curable resin according to this embodiment is 0.05 to 10.0 parts by mass with respect to 100 parts by mass of the energy beam curable urethane acrylate. In particular, it is preferably 0.1 to 6.0 parts by mass, and more preferably 0.5 to 4.0 parts by mass.
  • the energy beam curable resin according to the present embodiment is various additives such as a crosslinking agent, a silane coupling agent, a tackifier, and an antioxidant within a range that does not impair the object of the present invention.
  • An agent, an ultraviolet absorber, a light stabilizer, a softener, a filler, a colorant, a dispersant and the like may be contained as desired.
  • the energy beam curable resin according to the present embodiment contains the appropriate amount of the crosslinking agent, so that the energy beam curable hydrophilic pressure-sensitive adhesive composition described above. Therefore, the elongation at break and the stress relaxation rate can be adjusted, and the respective requirements can be easily satisfied.
  • crosslinking agent there is no restriction
  • crosslinking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, aziridine compounds, metal chelate compounds, metal alkoxides, and metal salts. Isocyanate compounds are preferably used.
  • polyisocyanate compound examples include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, and the like.
  • aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate
  • aliphatic polyisocyanates such as hexamethylene diisocyanate
  • alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate
  • biuret bodies, isocyanurate bodies, and adduct bodies that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glyco
  • the content (based on solid content) of the crosslinking agent in the energy ray curable resin according to this embodiment is 0.01 to 0.4 parts by mass with respect to 100 parts by mass of the (meth) acrylic acid ester copolymer.
  • the amount is preferably 0.03 to 0.3 parts by mass, and more preferably 0.05 to 0.25 parts by mass.
  • the composition of the particulate hydrophilicity imparting agent contained in the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to this embodiment is the above-mentioned requirements for mechanical properties (breaking elongation and stress relaxation rate) and the pressure-sensitive adhesive cured layer. It is optional as long as it meets the above-mentioned charging characteristics (charge voltage half-life) requirements that are sometimes required under predetermined conditions.
  • the “metal oxide” in the present embodiment means a compound containing a metal element and oxygen. When the metal element and oxygen are not in a stoichiometric composition, for example, a metal oxide having a stoichiometric composition is used. This includes those doped with other elements or compounds. Further, it may be a composite of a plurality of types of oxides (double oxide), and the oxide constituting the double oxide may contain a nonmetallic oxide.
  • the particulate hydrophilicity imparting agent comprising the metal oxide according to the present embodiment include tin-doped indium oxide (ITO) powder, gallium-doped zinc oxide (GZO) powder, antimony-doped tin oxide powder, zinc oxide and antimony pentoxide. And a double oxide containing phosphoric acid-doped tin oxide.
  • the conductive fine particles made of the metal oxide according to this embodiment are one or two selected from the group consisting of double oxides made of zinc oxide and antimony pentoxide, phosphoric acid doped tin oxide and tin doped indium oxide. It is preferable to contain seeds or more.
  • the upper limit of the particle diameter of the particulate hydrophilicity imparting agent according to this embodiment is not particularly limited.
  • the average particle diameter is preferably 1000 nm or less, and preferably 500 nm or less. Is more preferable, and 100 nm or less is particularly preferable.
  • the lower limit of the particle diameter of the particulate hydrophilicity imparting agent according to this embodiment is not particularly limited.
  • the average particle size of the particulate hydrophilicity imparting agent according to this embodiment is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more. .
  • the content of the particulate hydrophilicity imparting agent in the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment is such that the surface of the structure obtained by three-dimensionally molding the hydrophilic pressure-sensitive adhesive composition according to the present embodiment.
  • the degree of hydrophilicity to be possessed, the hydrophilicity imparting ability of the particulate hydrophilicity imparting agent itself, the shape of the structure to be obtained by three-dimensional molding (in other words, the degree of deformation by three-dimensional molding), etc. should be set as appropriate. Is.
  • the content of the particulate hydrophilicity imparting agent in the energy ray curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment is shown in the case where the particulate hydrophilicity imparting agent is composed of phosphate-doped tin oxide, It is 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and more preferably 15 to 45 parts by mass with respect to 100 parts by mass of the energy ray curable resin. Further preferred.
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to this embodiment is obtained by mixing the particulate hydrophilicity imparting agent and the energy ray-curable resin, and this hydrophilic pressure-sensitive adhesive composition.
  • the sol in which the metal oxide powder is dispersed in the liquid is used as the particulate hydrophilicity imparting agent according to the present embodiment, so that the particulate hydrophilic property in the obtained hydrophilic pressure-sensitive adhesive composition is used. It is preferable from the viewpoint of enhancing the dispersibility of the imparting agent.
  • Adhesive sheet] 1 A of adhesive sheets provided with the layer formed from the energy-beam curable hydrophilic adhesive composition which concerns on this embodiment are shown in FIG. 1, in order from the bottom on the peeling sheet 12 and the peeling surface of the peeling sheet 12. It is comprised from the laminated adhesive layer 11 and the base material 13 laminated
  • the adhesive sheet 1B provided with the layer formed from the energy-beam curable hydrophilic adhesive composition which concerns on this embodiment, as shown in FIG. 2, two release sheets 12a and 12b, and those two sheets
  • the adhesive layer 11 is sandwiched between the two release sheets 12a and 12b so as to be in contact with the release surfaces of the release sheets 12a and 12b.
  • the release surface of the release sheet in this specification refers to a surface having peelability in the release sheet, and includes both a surface that has been subjected to a release treatment and a surface that exhibits peelability without being subjected to a release treatment. .
  • the pressure-sensitive adhesive layer 11 is formed by forming the aforementioned energy ray-curable hydrophilic pressure-sensitive adhesive composition into a sheet shape.
  • the thickness of the pressure-sensitive adhesive layer 11 is appropriately determined according to the molding method of the pressure-sensitive adhesive sheet 1 and is usually in the range of 1 to 300 ⁇ m, preferably 5 to 100 ⁇ m, particularly preferably 10 to 50 ⁇ m.
  • polyester film such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, cellulose film such as triacetyl cellulose, polyurethane film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene- Plastic films such as vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene resin film, cycloolefin resin film; foams such as urethane foam and polyethylene foam; fine paper, glassine paper, impregnation Paper such as paper and coated paper; Metal foil such as aluminum and copper; Weaving using fibers such as rayon, acrylic and polyester Or nonwoven; and the like of two or more kinds of those laminates.
  • the plastic film may be uniaxially stretched or biaxially
  • the thickness of the substrate 13 varies depending on the type of material and the purpose of the pressure-sensitive adhesive sheet 1 and is not particularly limited, but is usually 10 to 300 ⁇ m, preferably 20 to 150 ⁇ m, and particularly preferably 35 to 80 ⁇ m.
  • release sheets 12, 12a, 12b for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, Polybutylene terephthalate film, polyurethane film, ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film A fluororesin film or the like is used. These crosslinked films are also used. Furthermore, these laminated films may be sufficient.
  • the release surface of the release sheet (particularly the surface in contact with the pressure-sensitive adhesive layer 11) is preferably subjected to a release treatment.
  • the release agent used for the release treatment include alkyd, silicone, fluorine, unsaturated polyester, polyolefin, and wax release agents.
  • the materials of the two release sheets 12a and 12b may be the same or different.
  • the release sheet 12a and the release sheet 12b are preferably adjusted so that the difference in release force is different, that is, one is a heavy release type release sheet and the other is a light release type release sheet.
  • the thickness of the release sheets 12, 12a and 12b is not particularly limited, but is usually about 20 to 150 ⁇ m.
  • the method for producing the pressure-sensitive adhesive sheet 1A is arbitrary.
  • a coating solution containing the energy ray-curable hydrophilic pressure-sensitive adhesive composition is applied to the release surface of the release sheet 12 and dried to form the pressure-sensitive adhesive layer 11, and then the pressure-sensitive adhesive layer 11.
  • the substrate 13 is laminated on the substrate.
  • the method of manufacturing the said adhesive sheet 1B is arbitrary. For example, after the application solution containing the energy ray-curable hydrophilic adhesive composition is applied to the release surface of one release sheet 12a (or 12b) and dried to form the adhesive layer 11 The release surface of the other release sheet 12b (or 12a) is superimposed on the adhesive layer 11.
  • a bar coating method for example, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, or the like can be used.
  • the release sheet 12 of the adhesive sheet 1A may be omitted, or one of the release sheets 12a and 12b in the adhesive sheet 1B may be omitted.
  • three-dimensional molding refers to a predetermined shape by three-dimensionally extending a processing target (energy ray-curable hydrophilic pressure-sensitive adhesive composition or pressure-sensitive adhesive layer 11 composed thereof).
  • Means a shape creation means for forming Specific means for three-dimensionally extending the object to be processed include a method of bringing a fluid or solid having a predetermined kinetic energy into contact with the object to be processed (blow molding and press molding are specific examples), and raw materials. Examples thereof include a method of holding the composition with a plurality of holding members and relatively changing their holding positions (partial stretch molding or torsion molding is a specific example).
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment and the pressure-sensitive adhesive layer 11 formed by forming this energy ray-curable hydrophilic pressure-sensitive adhesive composition into a sheet form are highly three-dimensionally stretched by three-dimensional molding. It is particularly suitable for three-dimensional molding because it has a high elongation at break that can correspond to the above and a sufficient stress relaxation rate that can stably maintain the shape created between the three-dimensional molding and the hardening by energy rays.
  • the hydrophilic adhesive composition or the adhesive layer 11 according to the present embodiment (hereinafter collectively referred to as “adhesive layer” in this description). .) Is attached to the base, and gas is supplied from the surface of the base facing the pressure-sensitive adhesive layer to a part of the interface between the pressure-sensitive adhesive layer and the base. Molding that extends a part away from the base to form a structure having a base, an adhesive interface between the base and the adhesive layer, and a hollow part formed by the extended adhesive layer Processing is also possible.
  • extension molding When energy ray curing is performed in this state, the stretched adhesive layer surrounding the hollow portion is cured, and the adhesive strength at the adhesive interface between the base and the adhesive layer is lowered. And a structure having sufficient strength can be easily removed from the base.
  • the three-dimensional molding by this method may be referred to as “extension molding”.
  • a method for supplying gas to the interface between the pressure-sensitive adhesive layer and the base has been shown as one specific example of a method for extending the pressure-sensitive adhesive layer three-dimensionally by extension molding.
  • the pressure-sensitive adhesive layer may be stretched three-dimensionally by other methods. Examples of such a method include a foaming agent-containing method, a protrusion push-up method, and a reduced pressure expansion method.
  • the shape of the stretch molding is not particularly limited, and may be, for example, a spherical shape, a hemispherical shape, a columnar shape, or a concavo-convex structure in which they are continuous.
  • the manufacturing method of the hydrophilic three-dimensional structure constituting the microreactor shown in FIG. 3 will be briefly described.
  • the base 21 having the surface on which the groove portion 21a corresponding to the shape of the microchannel is formed (FIG. 5A).
  • the pressure-sensitive adhesive layer 11 of the pressure-sensitive adhesive sheet 1 according to this embodiment is attached to the surface.
  • gas is supplied into, for example, the end portion 22a of the gas supply pipe 22 communicating with the groove portion 21a in the gap portion between the base 21 and the adhesive layer 11, that is, the groove portion 21a (see FIG. 5 (b)).
  • the adhesive layer 11 on the groove portion 21a expands due to the supplied gas, and the surface of the adhesive layer 11 opposite to the base 21 is partially raised (FIG. 5C).
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer 11 is cured.
  • a hydrophilic three-dimensional structure 23 that forms a microreactor is obtained (FIG. 5D).
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition according to the present embodiment when the pressure-sensitive adhesive layer 11 is formed from this composition, is subjected to JIS under the following measurement conditions.
  • the adhesive strength of the pressure-sensitive adhesive layer 11 measured according to Z0237 is preferably 5 N / 25 mm or more before curing and 1 N / 25 mm or less after curing. This adhesive strength is 9 N / 25 mm or more before curing, and more preferably 0.5 N / 25 mm or less after curing.
  • Adhesive sheet a pressure-sensitive adhesive layer 11 having a thickness of 20 ⁇ m formed on a film made of polyethylene terephthalate having a thickness of 25 ⁇ m
  • Substrate stainless steel plate, SUS304 # 360 Application time: 24 hours (23 ° C, 50RH)
  • the energy rays irradiated for curing the three-dimensionally shaped pressure-sensitive adhesive layer energy rays generated from various energy ray generators are used, and usually ultraviolet rays, electron beams and the like are used.
  • ultraviolet rays ultraviolet rays radiated from an ultraviolet lamp are usually used.
  • an ultraviolet lamp such as a high-pressure mercury lamp, a fusion H lamp, or a xenon lamp that emits ultraviolet light having a spectral distribution in a wavelength range of 300 to 400 nm is used, and the irradiation amount is usually 50 to 3000 mJ. / Cm 2 is preferred.
  • the irradiation dose is preferably about 10 to 1000 krad.
  • Example 1 Preparation of hydrophilic pressure-sensitive adhesive composition
  • a (meth) acrylic acid ester copolymer an acrylic acid ester copolymer obtained by copolymerizing 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid (weight average molecular weight 65 And 100 parts by mass (solid content) of an ethyl acetate / toluene mixed solvent, glass transition temperature of ⁇ 45 ° C., solid content concentration of 26% by mass, and energy ray curable urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Industry, UV- 6100B, weight average molecular weight 6700, glass transition temperature 0 ° C., pencil hardness 5B after curing) 100 parts by mass (solid content) and isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., Coronate L, solid content concentration 75% by mass) 0 .05 parts by mass (
  • a release surface of a light-release type release sheet (SP-PET 381031, thickness 38 ⁇ m, manufactured by Lintec Co., Ltd.) obtained by peeling one surface of a polyethylene terephthalate film with a silicone-based release agent was bonded.
  • the layer was sandwiched between two release sheets. Thereafter, the film was aged for 7 days under the conditions of 23 ° C. and 50% RH to obtain an adhesive sheet.
  • the thing with a dry film thickness of 5 micrometers was produced similarly.
  • Example 2 The (meth) acrylic acid ester copolymer contained in the energy ray-curable hydrophilic pressure-sensitive adhesive composition in Example 1 was mixed with 52 parts by mass of butyl acrylate, 20 parts by mass of methyl methacrylate, and 28 parts by mass of 2-hydroxyethyl acrylate.
  • Example 3 The particulate hydrophilicity imparting agent in Example 1 was changed to 20 parts by mass of zinc antimonate (manufactured by Nissan Chemical Industries, Cellax CX-Z210IP, average particle size 5-30 nm) in the same manner as in Example 2. An adhesive sheet was prepared.
  • Example 4 A pressure-sensitive adhesive sheet was obtained in the same manner as in Example 2, except that the particulate hydrophilicity imparting agent in Example 1 was changed to 40 parts by mass of indium tin oxide (ITO) powder (Mitsubishi Materials Electronics Chemical Co., Ltd., average particle size 30 nm). Produced.
  • ITO indium tin oxide
  • Example 1 instead of the particulate hydrophilicity imparting agent in Example 1, an adhesive sheet was prepared in the same manner as in Example 2 except that 10 parts by mass of an ionic liquid (tetra-n-octylphosphonium promide) was used as the hydrophilicity imparting agent. Produced.
  • an ionic liquid tetra-n-octylphosphonium promide
  • Example 2 The (meth) acrylic acid ester copolymer in the energy ray curable conductive pressure-sensitive adhesive composition in Example 2 was changed to 30 parts by mass (solid content) of acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., Dialnal BR-115), Instead of the energy ray curable urethane acrylate oligomer, 100 parts by mass (solid content) of dihydrocyclopentadiethyl acrylate (DCPA) was used. Except for these changes, an adhesive sheet was produced in the same manner as in Example 2.
  • DCPA dihydrocyclopentadiethyl acrylate
  • Example 3 In the composition of the energy ray-curable hydrophilic pressure-sensitive adhesive composition in Example 1, a pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that the particulate hydrophilicity imparting agent was not included.
  • the evaluation criteria for the observed resin shape are as follows. A: The resin shape is almost spherical. B: The resin shape did not swell more than the hemisphere or wrinkles occurred before it swelled into the hemisphere. C: The resin did not swell and the shape was not adjusted. Alternatively, it was destroyed when removed from the needle, or peeled off from the needle tip before swelling. The results are shown in Table 1.
  • the surface of the pressure-sensitive adhesive layer is affixed to the adherend and allowed to stand for 24 hours, and then irradiated with ultraviolet rays (illuminance 120 mW, light amount 70 mJ) by an ultraviolet irradiation device (FUSION, CV-110O-G).
  • the pressure-sensitive adhesive layer 31 was irradiated with ultraviolet rays (illuminance 120 mW, light amount 70 mJ) by using an ultraviolet irradiation device (FUSION, CV-110O-G) from the side of the heavy release sheet of the pressure-sensitive adhesive sheet, and cured.
  • An electrode sheet 34 having a configuration in which the layer 31, the ITO layer 32, and the PET film 33 were laminated in this order was produced.
  • another electrode sheet 34 is prepared.
  • these electrode sheets 34 have a gap 35 in which the opposite surfaces of the cured adhesive layer 31 to the ITO layer 32 are 50 ⁇ m.
  • the cell 30 for ion elution test was obtained so that it might oppose.
  • Silicone oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) was filled in the gap 35 of 50 ⁇ m in the ion elution test cell 30 in an environment of 23 ° C. and 50% RH.
  • the surface of the PET layer 33 opposite to the ITO layer 32 is used as an electrode of the ion elution test cell 30, and a constant voltage (15 kV) is applied to these surfaces. It is evaluated whether or not ions are difficult to elute from the cured adhesive layer 31 into the silicone oil depending on whether the change in the current value was almost not observed (A) or the current value increased (F). did.
  • F Increase in current value was confirmed
  • the energy ray-curable hydrophilic pressure-sensitive adhesive composition obtained in the Examples that satisfies the requirements of the present invention is excellent in three-dimensional moldability, and the cured product of such a composition has sufficient hydrophilicity. It was something to prepare.
  • hydrophilic structure formed by three-dimensionally molding the energy ray-curable hydrophilic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet of the present invention and further curing the energy ray is suitably used for applications requiring hydrophilicity such as a microreactor. can do.

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JP2016199609A (ja) * 2015-04-07 2016-12-01 株式会社イノアック技術研究所 粘着組成物および、粘着組成物の製造方法
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JP2017026579A (ja) * 2015-07-28 2017-02-02 株式会社朝日Ｆｒ研究所 マイクロ化学チップ及びその製造方法

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