TWI568813B - An energy ray-hardening type hydrophilic adhesive composition, an adhesive sheet, and a hydrophilic structure - Google Patents

Description

Energy line hardening type hydrophilic adhesive composition, adhesive sheet and hydrophilic structure

The present invention relates to an energy ray-curable hydrophilic adhesive composition and an adhesive sheet, and more particularly to an energy ray-curable hydrophilic adhesive composition suitable for three-dimensionally elongated three-dimensional forming and comprising the same An adhesive sheet of the adhesive layer, and a hydrophilic structure obtained from the adhesive composition or the adhesive layer.

The micro-machining technology has been used to miniaturize the entire system for chemical analysis, chemical synthesis, or bio-related analysis, and the modularization method has attracted attention. Such a module is called a μ TAS (Micro Total Analysis System) or a microreactor. Since the amount of the target substance to be analyzed or synthesized is small, the microreactor has the advantages of high efficiency of heating or cooling, and the advantage that the reaction length is fast because the diffusion length of the target substance is short. In addition, since the total amount of time is reduced, the time taken for analysis is shortened, and there is a benefit that can be quickly evaluated. Furthermore, even in the case where the equipment used for analysis or reaction is to be discarded, it is only necessary to discard the used modules in a complete group, so that there is a benefit of reducing the total cost of disposal.

Because of this benefit, many techniques related to microreactors have been proposed.

For example, Patent Document 1 discloses a micro-convergence structure having three or more inflow passages, a confluence portion in which the inflow passages merge, and one outflow passage extending in the downstream direction from the confluence portion. The manifold unit is configured such that one of the busbar units is disposed on the most downstream side, and the outflow path is an outlet of the minute bus path structure, and the outflow path of the remaining busbar unit becomes an inflow path of the busbar unit on the downstream side, and the rest The inflow path becomes the entrance to the tiny confluence structure.

Patent Document 2 discloses a wafer for biological sample reaction, comprising: a plurality of reaction vessels disposed on the same plane; and a reaction liquid introduction flow path, which is connected to each reaction container via a fine flow path, and is disposed in a majority The reaction liquid moving stop member is connected to the end portion of the reaction liquid introduction flow path, and the movement of the reaction liquid can be controlled.

Patent Document 3 discloses a micro flow path for supplying a liquid to a sensor or discharging a liquid that has been supplied to a sensor, characterized in that it has a flow path body to be used in an upright state to be parallel to a flow path. The first wall surface which is hydrophobic and the second wall surface which is hydrophilic are divided by the dividing surface of the center line, and the flow path body satisfies the condition expressed by a specific number using the shape of the flow path as a parameter.

As described above, many techniques have been proposed for the construction of microreactors, but the construction of such microreactors is premised on the application of microfabrication techniques which have hitherto been used in the manufacture of semiconductor elements, and most of the materials are used. Inorganic materials such as germanium or inorganic materials such as glass. For example, the material of the microreactor disclosed in Patent Document 2 is glass.

But from the point of view of improving productivity, some people have tried to use resin. As a material of the microreactor, for example, the microreactor disclosed in Patent Document 3 is composed of plastic and glass. In addition, the resin-based material refers to a resin component as one of the main components, and has the advantage that the entire material can enjoy the same level as the resin material (especially, the shape creation ability described later is high).

In response to such an attempt, a resin-based material for the purpose of a microreactor has also been proposed.

For example, Patent Document 4 discloses a synthetic resin composition comprising two or more kinds of synthetic resin components for forming a structure in which a two-dimensional or three-dimensional microchannel or a nanochannel is formed on a surface. The material, the first component is a polypropylene resin, and the second component is a hydrogenated derivative of the block copolymer.

Patent Document 5 discloses a material which is a resin-filler composite material for a resin substrate for a microreactor, an inorganic material or a polymer material having an aspect ratio of 10 or more, or a birefringence having a predetermined value or more. The polymer material of the ratio of the filler is 0.01 to 200 parts by weight based on 100 parts by weight of the resin.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-158650

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-136220

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-203003

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-264446

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-231427

The resin-based material which is a material of the microreactor has one of the advantages of other materials (for example, semiconductors such as germanium, inorganic materials such as glass, and metals), which are easier to create shapes than other materials, and the freedom of the shape that can be created. High degree. For example, if a resin-based material is a thermoplastic resin and an injection molding technique, a blow molding technique, or a press molding technique is applied, it is easier to manufacture a high aspect ratio concave than in the case of a microfabrication technique generally employed in the manufacture of a semiconductor device. Shape or complex height difference shape.

However, the resin-based material has a problem that its surface is generally hydrophobic. If it is considered that the liquid flowing through the microreactor is usually an aqueous solution (the biologically relevant application is almost entirely an aqueous solution), as long as the microreactor system disclosed in Patent Document 3 does not actively utilize its hydrophobicity, the microreactor is required to be at least Hydrophobic in the wetted surface.

Such a hydrophilization technique, for example, a surface modification represented by corona treatment or the like. However, it is not easy to uniformly perform surface modification on the liquid contact surface of the inner surface of the microreactor having a small and complicated structure.

Another method of hydrophilizing the liquid contact surface of the microreactor comprising a resin material is a method of including a hydrophilicity imparting agent in the resin material. The most common of such materials is a surfactant or an ionic liquid.

However, since the resin-based material containing a surfactant or an ionic liquid physically moves in the resin-based material, it is essentially impossible to prevent the ionic substance from being eluted from the resin-based material. Although it is possible to reduce the degree of dissolution, the fact of dissolution leads to the reliability of the analytical results. Declining, biologically relevant uses have concerns that affect living conditions. Therefore, a method of changing the physical properties of a resin-based material using a surfactant or an ionic liquid is applied to a microreactor, which is unacceptable in reality.

Further, in the investigation by the inventors of the present invention, it has been found that when the resin-based material contains an ionic liquid such as an imidazolium salt, the ionic substance contributes to the hydrophilization of the surface of the resin, but the substance becomes a resin-based material. The hindrance factor of the plastic deformability reduces the maximum advantage of using a resin-based material, that is, the shape-creating ability. In particular, in the case where the resin-based material containing an ionic liquid is three-dimensionally elongated to form a system of a predetermined shape, that is, in the case of three-dimensional molding, the degree of elongation of the resin-based material without breaking is markedly lowered.

An object of the present invention is to provide a resin material which is a constituent material of a fine structure which is hydrophilized on the surface represented by a microreactor, and more specifically, a resin composition or a resin composition is provided. Layer of the plate.

In order to solve the above problems, the first aspect of the invention provides an energy ray-curable hydrophilic adhesive composition (Invention 1) which comprises an energy ray-curable resin and is dispersed in the energy ray-curable resin. In the energy ray-curable hydrophilic adhesive composition, the energy ray-curable hydrophilic adhesive composition has an elongation at break of 2000% or more and a stress relaxation rate of 70% or more and 95% or less before the energy ray curing. The energy ray-curable hydrophilic adhesive composition is formed into a 20 μm thick adhesive layer formed on a polyethylene terephthalate resin sheet having a thickness of 38 μm, and the adhesive layer is energy-hardened to obtain an adhesive layer. When using an adhesive hardening layer, the use of a half-life measuring machine as defined in JIS L1094:1997 The half-life of the measured static voltage is 25 ° C and 50% RH is 60 seconds or less.

Here, the "hydrophilic property" in the energy ray-curable hydrophilic adhesive composition means that the surface of the cured product obtained by energy-hardening the adhesive composition is hydrophilic.

Since the hydrophilicity-imparting agent is in the form of particles, the hydrophilicity-imparting agent is desorbed from the structure in use, and the hydrophilicity of the surface of the structure is lowered or the substance (for example, a reaction liquid) that contacts the structure is contaminated. Further, since the energy ray-curable resin has a sufficiently high elongation at break before curing, a three-dimensional structure having various shapes can be obtained. By performing energy ray hardening of the three-dimensional structure, a hydrophilic structure suitable for use as a microreactor or the like can be obtained.

In the above invention (Invention 1), it is preferred that the average particle diameter of the particulate hydrophilicity-imparting agent is 1000 nm or less (Invention 2). When the average particle diameter is 1000 nm or less, the surface roughness of the hydrophilic solid structure obtained by energy ray hardening is reduced, and excellent surface properties are easily obtained.

In the above inventions (Inventions 1 and 2), it is preferred that the particulate hydrophilicity-imparting agent is composed of a metal oxide (Invention 3). Since the particulate hydrophilicity imparting agent composed of the metal oxide is excellent in optical characteristics, when the energy ray-curable hydrophilic adhesive composition is cured, the occurrence of hardening variation can be reduced. Further, it is easy to observe the content (for example, a reaction liquid) of the hydrophilic solid structure obtained by energy beam hardening.

In the above invention (Inventions 1 to 3), the metal oxide preferably contains one or more selected from the group consisting of a complex oxide composed of tin oxide doped with phosphoric acid, zinc oxide and antimony pentoxide. Preferably (Invention 4). These metal oxides are particularly excellent in optical characteristics.

In the above invention (Inventions 1 to 4), when the energy ray-curable hydrophilic adhesive composition is formed into a 5 μm thick adhesive layer, it is preferable that the total light transmittance before the energy ray hardening is 80% or more. Further, the haze of the pressure-sensitive adhesive layer is preferably 10% or less (Invention 5). By having such excellent optical characteristics, it is possible to particularly reduce the possibility of occurrence of hardening deviation of the above composition, and it is easy to observe the contents of the cured hydrophilic solid structure.

In the above invention (Inventions 1 to 5), the energy ray-curable resin preferably contains a (meth) acrylate copolymer and an energy ray-curable urethane acrylate (Invention 6). By containing the relevant material, the composition before hardening easily satisfies the aforementioned mechanical properties.

In the above invention (Invention 6), the content of the energy ray-curable urethane acrylate is preferably 50 to 200 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer (Invention 7). . By having such a composition, the composition can be sufficiently cured, and at the same time, the shape can be easily maintained when the composition is formed into a sheet shape or the like.

In the above invention (Inventions 6, 7), the glass transition temperature (Tg) of the (meth) acrylate copolymer before energy ray hardening is -50 to 0 ° C, and the energy ray-curable urethane acrylate is The glass transition temperature (Tg) after the energy ray hardening is preferably -40 to 20 ° C (Invention 8). By having such a composition, it is possible to achieve an appropriate balance between the adhesion and the breaking strength of the energy ray-curable resin.

In the above invention (Inventions 6 to 8), it is preferable that the energy-hardening urethane acrylate has a pencil hardness of B to 5B after energy beam curing (Invention 9). By including this mechanical property, the shape of the hydrophilic solid structure can be maintained to be good, and the possibility that the obtained structure is brittle fracture can be reduced.

The energy ray-curable hydrophilic adhesive composition of the above invention (Inventions 1 to 9) is preferably used for stereoscopic molding (Invention 10). As described above, the energy ray-curable hydrophilic adhesive composition of the present invention is excellent in hardenability and excellent in mechanical properties before and after curing. It is therefore suitable as a material for performing three-dimensional forming.

In the above invention 10, the energy ray-curable hydrophilic adhesive composition may be three-dimensionally elongated to perform three-dimensional molding (Invention 11). Even if the composition is elongated in three dimensions, the elongation at break is excellent before curing, so that the composition is less likely to undergo aggregation failure during the process, and the stress relaxation rate before curing is within an appropriate range, and it is difficult to be in a period from elongation to hardening. A shape change has occurred.

According to a second aspect of the invention, there is provided an adhesive sheet comprising the energy ray-curable hydrophilic adhesive composition according to any one of the inventions (Inventions 1 to 11).

In the adhesive sheet, the composition of any of the above inventions (Inventions 1 to 11) is excellent in mechanical properties in a state before curing, so that it is easy to maintain its shape, and it is less likely to cause aggregation failure when the adhesive sheet is three-dimensionally formed. And other issues. Furthermore, since the adhesive sheet has hydrophilicity, a hydrophilic three-dimensional structure can be obtained.

According to a third aspect of the invention, there is provided an adhesive sheet comprising the energy ray-curable hydrophilic adhesive composition according to any one of the above inventions (Inventions 1 to 11), and Two peeling sheets of the aforementioned adhesive layer are sandwiched.

The adhesive sheet can appropriately protect the adhesive layer composed of the composition of any one of the above inventions (Inventions 1 to 11) until it is attached to the adherend Therefore, the adhesion to the surface of the bonding surface of the adherend or the possibility of contamination of the surface can be reduced.

According to a fourth aspect of the present invention, a hydrophilic structure (Invention 14) is characterized in that the energy ray-curable hydrophilic adhesive composition of any one of the above inventions (Inventions 1 to 11) is three-dimensionally elongated It is obtained by three-dimensional forming.

The energy ray-curable hydrophilic adhesive composition according to any one of the inventions (1 to 11) has excellent mechanical properties, and thus the hydrophilic structural body obtained by stereoscopically molding the composition can have various shapes. .

According to a fifth aspect of the invention, there is provided a hydrophilic structure (Invention 15) characterized in that the adhesive layer in the adhesive sheet of any one of the inventions (Inventions 12 and 13) is three-dimensionally elongated. Stereoformed.

The energy ray-curable hydrophilic adhesive composition constituting the adhesive layer in the adhesive sheet of any of the above inventions (Inventions 12 and 13) has excellent mechanical properties, so that the composition is stereoformed to obtain a hydrophilic The sexual constructs can have a variety of shapes.

The energy ray-curable hydrophilic adhesive composition of the present invention has a particulate hydrophilicity imparting agent, and the surface of the structure (for example, a microreactor) obtained from the composition is hydrophilic by the particulate hydrophilicity imparting agent. Chemical. By using the particulate hydrophilicity-imparting agent, it is possible to suppress the hydrophilicity of the surface of the structure from the structure in use to the detachment of the hydrophilicity-imparting agent, or to contaminate the substance (for example, a reaction liquid) which contacts the structure. Moreover, since the elongation at break before the energy ray hardening is sufficiently high, it is possible to easily form a general semiconductor by stereolithography. Shapes implemented by the related microfabrication technology are complex shapes that are difficult to form during processing, such as a shape having a large aspect ratio. The three-dimensional structure obtained in this manner is subjected to energy ray hardening to obtain a hydrophilic structure having high mechanical strength, and the structure is suitable for use as a microreactor or the like.

1A, 1B‧‧‧Adhesive sheets

11‧‧‧Adhesive layer

12,12a,12b‧‧‧ peeling sheets

13‧‧‧Substrate

14‧‧‧Micro Syringes

15‧‧‧UV irradiation device

21‧‧‧Abutment

21a‧‧‧Ditch section

22‧‧‧ gas supply pipe

22a‧‧‧End opening

23‧‧‧Hydrophilic solid structure

30‧‧‧Ion Dissolution Test Unit

31‧‧‧Adhesive layer

32‧‧‧Indium Tin Oxide (ITO) Layer

33‧‧‧Polyethylene terephthalate (PET) film

34‧‧‧Electrode plates

35‧‧‧The gap between the plates for electrodes

Fig. 1 is a cross-sectional view showing an example of an adhesive sheet including an adhesive layer formed of an adhesive composition according to an embodiment of the present invention.

Fig. 2 is a cross-sectional view showing another example of an adhesive sheet comprising an adhesive layer formed of the adhesive composition of the embodiment of the present invention.

Fig. 3 is a conceptual schematic view showing an example of a process of obtaining a hydrophilic solid structure having a shape of a minute flow path by stereoscopically molding an adhesive composition according to an embodiment of the present invention.

Fig. 4 is a view showing the procedure for evaluating the elongation formability in Test Example 6.

Fig. 5 is a conceptual schematic cross-sectional view showing a cross section of an ion elution test cell for performing the ion elution test in Test Example 8.

Hereinafter, embodiments of the present invention will be described.

[Energy curing type hydrophilic adhesive composition]

The energy ray-curable hydrophilic adhesive composition of the present embodiment (hereinafter referred to simply as "hydrophilic adhesive composition" or "adhesive composition") is the elongation at break and stress before energy ray hardening. If the relaxation rate satisfies the following requirements, it is suitable for a three-dimensional shape due to these characteristics.

Here, the "three-dimensional forming" in the present application is processed by The target material is three-dimensionally elongated to form a shape of a predetermined shape, and the term "elongation" also encompasses the concept of expansion.

The energy ray-curable hydrophilic adhesive composition of the present embodiment has an elongation at break of 2000% or more. The elongation at break is measured by processing the hydrophilic adhesive composition together with the substrate or the like into a separate adhesive layer, specifically, a thickness of 500 μm, a width of 15 mm, and a length of 55 mm (wherein the measurement range) The hydrophilic adhesive composition of 25 mm) was extruded at a rate of 200 mm/min in an environment of 23 ° C and 50% RH.

The energy relaxation ratio of the energy ray-curable hydrophilic adhesive composition of the present embodiment is 70 to 95%, preferably 75 to 93%, and particularly preferably 80 to 91%. When the stress relaxation rate is 70% or more, it is easy to maintain the hydrophilic adhesive composition in an elongated state, and it is easy to form into a desired shape. Further, when the stress relaxation ratio is 95% or less, when the hydrophilic adhesive composition is kept in an extended state, it is possible to suppress further deformation of the shape by a force other than the force of elongation (for example, gravity).

The stress relaxation ratio refers to the ratio of the stress of the hydrophilic adhesive composition at 300% elongation in the tensile test to the stress at the time of holding 300 seconds. The stretching conditions, specifically, the hydrophilic adhesive composition formed into a thickness of 500 μm, a width of 15 mm, and a length of 55 mm (including a measurement range of 25 mm) were set at a rate of 200 mm/min in an environment of 25 ° C and 50% RH. The elongation is 300% and the implementer. The stress relaxation rate is calculated based on the stress A at 300% elongation and the stress B after 300 seconds from the stop of elongation.

Stress relaxation rate (%) = {(A-B) / A) × 100 (%)

The surface of the cured product obtained by energy ray hardening from the energy ray-curable hydrophilic adhesive composition of the present embodiment is hydrophilic, and An adhesive layer having a thickness of 20 μm composed of the hydrophilic adhesive composition of the present embodiment was formed on a polyethylene terephthalate resin sheet having a thickness of 38 μm, and the adhesive layer was subjected to energy ray hardening. Adhesive hardening layer, the half-life of the static voltage measured by the half-life measuring device defined by JIS L1094:1997 (after the charging by corona discharge, the static voltage is attenuated to 25 ° C, 50% RH until 1/2 time ) is 60 seconds or less.

When the half life is 60 seconds or less, the surface of the adhesive hardened layer is sufficiently hydrophilic to suppress the occurrence of defects due to insufficient hydrophilicity. Specific examples of the above-described problem include that the liquid does not enter the concave portion of the microstructure, and the predetermined reaction that is scheduled to be performed in the concave portion does not proceed at this time, and there is no liquid in the concave portion of the measurement portion, and such a problem cannot be analyzed. . Further, the flow path is turbulent, and the occurrence of the bubble entrapment is also an example of the above-described problem. In this case, the flow control of the reaction is insufficient, and the reaction is not performed as scheduled. When the optical characteristics of the liquid are measured, information on the bubble is added. There is a problem that the reliability of the measurement result is lowered.

In the case where the above half-life is 45 seconds or less, the surface of the adhesive hardened layer has particularly excellent hydrophilicity, and it is possible to achieve a more stable avoidance of the above-mentioned undesirable phenomenon.

In addition, the contact angle of the droplet formed on the flat resin material to be evaluated is generally used as a hydrophilicity evaluation method. However, since the hydrophilic adhesive composition of the present embodiment contains a particulate hydrophilicity imparting agent, The shape (particle diameter, etc.) of the particulate hydrophilicity-imparting agent may cause irregularities on the surface of the above-mentioned adhesive hardened layer. In this case, the interface between the droplet and the resin material is not flat, and the reliability is lowered even if the contact angle of the droplet is measured. Therefore, in this case, it is not appropriate to use the contact angle as a criterion for judging whether or not the surface of the adhesive hardened layer is sufficiently hydrophilic. In contrast, the above half-life Since the measurement result is hardly affected by the surface properties of the adhesive hardened layer, the degree of hydrophilicity can be determined stably and quantitatively.

In the energy ray-curable hydrophilic adhesive composition of the present embodiment, when a layer having a thickness of 5 μm is formed, the total light transmittance according to JIS K7361-1:1997 is preferably 80% or more before the energy ray hardening. . Further, the haze of the above-mentioned adhesive layer according to JIS K7136:2000 is preferably 10% or less before the energy ray hardening. In the case where these optical characteristics are included, even if the structure is formed into a three-dimensional shape by stereoscopic molding, the energy rays irradiated to the entire structure can be stably reached. Therefore, by having such optical characteristics, it is possible to safely prevent a local decrease in the mechanical properties of the structure after hardening.

The energy ray-curable hydrophilic adhesive composition of the present embodiment is a hydrophilic adhesive composition containing an energy ray-curable resin and a particulate hydrophilicity-imparting agent dispersed in the energy ray-curable resin. Hereinafter, the composition of the energy ray-curable resin and the particulate hydrophilicity-imparting agent will be described in detail.

[Energy curing resin]

The composition of the energy ray-curable resin of the present embodiment is arbitrary as long as the energy ray-curable hydrophilic adhesive composition before curing satisfies the above mechanical properties (elongation at break and stress relaxation rate). The energy ray-curable resin of the present embodiment preferably contains (1) a (meth) acrylate copolymer and (2) an energy ray-curable urethane acrylate, and further contains (3) a photopolymerization initiator. Especially good. The energy ray-curable resin of the present embodiment may contain (4) other components such as a crosslinking agent.

(1) (meth) acrylate copolymer

The (meth) acrylate copolymer is not particularly limited, and a (meth) acrylate which is conventionally used as a resin component of a conventional acrylic adhesive composition can be suitably selected. Any of the polymers. Such a (meth) acrylate copolymer, for example, an alkyl (meth) acrylate having a carbon number of 1 to 20, a monomer having a functional group having an active hydrogen, and other monomers as needed The body formed copolymer is preferred. Further, (meth) acrylate means both acrylate and methacrylate. Other similar terms are the same.

An alkyl (meth) acrylate having a carbon number of 1 to 20, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate Ester, butyl (meth)acrylate, octyl (meth)acrylate, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, cyclomethacrylate Ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, myristyl (meth)acrylate, ( Methyl) palmitate, stearyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

On the other hand, a monomer having a functional group having active hydrogen, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, Hydroxyalkyl (meth)acrylate such as 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, monomethylamine (meth)acrylate Alkyl (meth)acrylic acid monoalkylamine such as ethyl ethyl ester, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate or monoethylaminopropyl (meth)acrylate An alkyl ester; an ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or citraconic acid. These monomers may be used alone or in combination of two or more.

Further, other monomers to be used, such as vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene, and isobutylene; Halogenated olefins such as olefin and vinylidene chloride; styrene monomers such as styrene and α-methylstyrene; diene monomers such as butadiene, isoprene and chloroprene; acrylonitrile And a nitrile monomer such as methacrylonitrile; an acrylamide such as acrylamide, N-methyl acrylamide or N,N-dimethyl acrylamide. These may be used alone or in combination of two or more.

Among them, among the above (meth) acrylate copolymers, those having an energy ray polymerizable group in the molecule (so-called adduct polymer) are preferred. The method of bringing the energy ray polymerizable group in the molecule of the (meth) acrylate copolymer is not particularly limited, and for example, by (meth) acrylate copolymer (a1) having a monomer unit having a functional group, It is obtained by reacting an unsaturated group-containing compound (a2) having a substituent reactive with the functional group.

(a1) The functional group-containing monomer contained in the component (a1) is preferably a hydroxyl group such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate or 2-hydroxypropyl methacrylate. Acrylate is preferred.

The component (a2) is preferably a compound having a functional group reactive with a hydroxyl group of the component (a1) and a polymerizable double bond, for example, methyl methacrylate isocyanate or methyl isopropenyl isocyanate. α,α-dimethylbenzyl ester, methacrylic acid methacrylate, allyl isocyanate, glycidyl (meth)acrylate; (meth)acrylic acid.

When a (meth) acrylate copolymer having an energy ray polymerizable group in a molecule is used, the amount of the energy ray-curable urethane acrylate which is a low molecular weight component can be reduced, so that the low molecular weight component can be reduced from hydrophilic The adhesive composition exuded. If the bleed out is suppressed, the composition change of the hydrophilic adhesive composition does not change, and the deterioration of the adhesive strength of the design does not occur, and at this time, the hydrophilic adhesive composition can be suppressed from the abutment at the time of elongation molding described later. Stripped. So will The (meth) acrylate copolymer having an energy ray polymerizable group in the molecule is preferably used as the component (a2).

The copolymerization form of the (meth) acrylate copolymer is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer.

The molecular weight of the (meth) acrylate copolymer is preferably 300,000 or more, more preferably 350,000 to 2,500, based on the weight average molecular weight. When the weight average molecular weight is less than 300,000, the adhesion to the adherend or the durability of the adhesive becomes insufficient. The weight average molecular weight of the (meth) acrylate copolymer is preferably from 400,000 to 1.8,000,000, in view of adhesiveness, durability, and the like. In the present specification, the weight average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the (meth) acrylate copolymer before the energy ray hardening is preferably -50 to 0 ° C, more preferably -40 to 0 ° C. The glass transition temperature (Tg) of the (meth) acrylate copolymer can achieve a moderate balance of adhesion and elongation at break by this range. Therefore, when the structure is obtained by shape creation by elongation molding described later, it is preferable to set the glass transition temperature (Tg) of the (meth) acrylate copolymer before the energy ray hardening as described above.

(2) Energy line hardening urethane acrylate

An energy ray-hardening urethane acrylate is an oligomer compound having a (meth) acrylonitrile group and a urethane bond, and has a (meth) acrylonitrile group in the molecule, so that it can be used for energy ray The structure obtained by the three-dimensional forming by the polymerization hardening imparts high mechanical strength.

Energy line hardening urethane acrylate, for example by The polyisocyanate compound is obtained by reacting a (meth) acrylate having a hydroxyl group or an isocyanate group with a polyol compound. As the energy ray-curable urethane acrylate, for example, a terminal isocyanate group-containing urethane prepolymer obtained by reacting a polyol compound with a polyisocyanate compound, and further having a hydroxyl group (meth)acrylic acid The urethane acrylate obtained by the ester reaction, or the urethane prepolymer containing a terminal hydroxyl group obtained by reacting the polyol compound with the polyisocyanate compound, further obtains the (meth) acrylate having an isocyanate group. A urethane acrylate.

Polyisocyanate compounds, for example: isophorone diisocyanate, 2,4-tolyl diisocyanate, 2,6-tolyl diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene Diisocyanate such as diisocyanate or diphenylmethane-4,4'-diisocyanate.

a (meth) acrylate having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylic acid 4-hydroxybutyl ester, polyethylene glycol (meth) acrylate, and the like. A (meth) acrylate having an isocyanate group, for example, methacrylic acid ethyl methacrylate.

The polyol compound is, for example, a polyol compound such as an alkylene type, a polycarbonate type, a polyester type or a polyether type, specifically, for example, polyethylene glycol, polypropylene glycol, polytetramethylene Alcohol, polycarbonate diol, polyester diol, polyether diol, and the like.

As the energy ray-curable urethane acrylate, a commercially available product can also be used. For example: U-200PA, UA-4200, manufactured by Shin-Nakamura Industrial Co., Ltd., AU-3110, AU-3120, manufactured by TOKUSHIKI Co., Ltd., Japan Synthetic Chemistry Violet UV-6100B, UV-3210EA, UV-6010EA, UV-6020EA, EBECRYL 210, 230, manufactured by CYTEC DAICEL Co., Ltd., manufactured by Industrial Co., Ltd.

The above-mentioned 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-hardening urethane acrylate is preferably from 1,000 to 12,000, particularly preferably from 2,500 to 10,000, more preferably from 4,000 to 8,000. When the weight average molecular weight is 1,000 or more, the obtained hydrophilic adhesive composition can obtain a sufficient elongation at break, and if it is 12,000 or less, the hydrophilic adhesive composition is plated (formed of a hydrophilic adhesive composition). Adhesive layer) exhibits optimum viscosity.

The glass transition temperature (Tg) of the energy ray-hardening urethane acrylate after energy line hardening is preferably -40 to 20 ° C, especially -20 to 10 ° C. By setting the glass transition temperature (Tg) of the energy ray-curing urethane acrylate to this range, an appropriate balance of adhesion and elongation at break can be achieved. Therefore, when the shape is created by elongation molding described later to obtain a structure, it is preferable to set the glass transition temperature (Tg) of the energy ray-curable urethane acrylate after energy ray hardening as described above. Further, the glass transition temperature (Tg) of the energy ray-curable urethane acrylate is a value after energy ray hardening, which is irradiated with ultraviolet rays (illuminance: 80 mW/cm, cumulative light amount: 800 mJ/cm ² ) and then differentially scanned. Calorimetric (DSC method) measured value.

The pencil hardness of the energy ray-hardened urethane acrylate is preferably B~5B, more preferably 3B~5B, more preferably 4B~5B, and most preferably 5B. If the pencil hardness is 5B and the equivalent is hard, hard The hydrophilic adhesive composition after the formation has sufficient hardness to maintain the shape well. When the pencil hardness is softer than 5B, the shape cannot be maintained, and it becomes impossible to form a three-dimensional shape. Further, if the pencil hardness is B or less, the hydrophilic adhesive composition after curing is not brittle, so that the brittle fracture of the structure composed of the hydrophilic adhesive composition can be suppressed. In particular, when the structure is obtained by the elongation molding described later, the structure is obtained, and when the hydrophilic adhesive composition after the hardening is separated from the base, the structure having the above-described hardness characteristics can suppress the occurrence of the structure during the operation. Damaged, it is ideal.

In the energy ray-curable resin of the present embodiment, the content of the energy ray-curable urethane acrylate (solid content basis) is preferably 50 to 200 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer. Preferably, it is preferably 70 to 180 parts by mass, more preferably 80 to 150 parts by mass. When the content of the energy ray-curable urethane acrylate is 50 parts by mass or more, the hydrophilic adhesive composition obtained can have sufficient curability, and if it is 200 parts by mass or less, the high molecular weight component can be sufficiently ensured ( The content of the methyl acrylate copolymer maintains the shape when the hydrophilic adhesive composition is stored in a sheet state.

(3) Photopolymerization initiator

The energy ray-curable resin of the present embodiment can reduce the irradiation amount and the irradiation time of the energy ray-curable urethane acrylate required for polymerization hardening by containing a photopolymerization initiator.

The photopolymerization initiator is not particularly limited, and examples thereof include diphenyl ketone, acetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, Benzene benzoic acid, methyl benzoin benzoate, benzoin dimethyl acetal, 2,4-diethyl thioxanthone, 1-hydroxycyclohexyl phenyl ketone, benzyl di Oxidation of phenyl sulfide, tetramethylthiuram monosulfide, azobisisobutyronitrile, 2-chloroindole, diphenyl (2,4,6-trimethylbenzhydryl) Phosphine and the like. These photopolymerization initiators may be used alone or in combination of two or more.

In the energy ray-curable resin of the present embodiment, the content of the photopolymerization initiator (solid content basis) is preferably 0.05 to 10.0 parts by mass based on 100 parts by mass of the energy ray-curable urethane acrylate. Preferably, it is 0.1 to 6.0 parts by mass, more preferably 0.5 to 4.0 parts by mass.

(4) Other ingredients

The energy ray-curable resin of the present embodiment may contain various additives such as a crosslinking agent, a decane-based coupling agent, an adhesion-imparting agent, an antioxidant, an ultraviolet absorber, and the like, without departing from the object of the present invention. Light stabilizer, softener, filler, colorant, dispersant, and the like.

In the other components, the energy ray-curable resin of the present embodiment can adjust the elongation at break required for the energy ray-curable hydrophilic adhesive composition by appropriately containing a crosslinking agent. Degree and stress relaxation rate, easy to meet various requirements.

The crosslinking agent is not particularly limited, and may be appropriately selected from any of the conventionally used acrylic resins as a crosslinking agent. Such a crosslinking agent, for example, a polyisocyanate compound, an epoxy resin, a melamine resin, a urea resin, a dialdehyde, a methylol polymer, an aziridine compound, a metal chelate compound, a metal alkoxide, a metal salt, or the like, However, polyisocyanate compounds are preferred.

Polyisocyanate compounds, for example, aromatic polyisocyanates such as tolyl diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate An aliphatic polyisocyanate such as an acid ester or hexamethylene diisocyanate, an alicyclic polyisocyanate such as isophorone diisocyanate or hydrogenated diphenylmethane diisocyanate, or the like, and a biuret or isocyanuric acid. The ester body and an adduct of a reactant of a low molecular weight active hydrogen-containing compound such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil. These crosslinking agents may be used alone or in combination of two or more.

In the energy ray-curable resin of the present embodiment, the content of the crosslinking agent (based on the solid content) is preferably 0.01 to 0.4 parts by mass, more preferably 0.03%, per 100 parts by mass of the (meth) acrylate copolymer. 0.3 parts by mass, more preferably 0.05 to 0.25 parts by mass.

[Particulate hydrophilicity imparting agent]

The composition of the particulate hydrophilicity-imparting agent contained in the energy ray-curable hydrophilic adhesive composition of the present embodiment is satisfied by the requirements of the mechanical properties (elongation at break and stress relaxation rate) and the hardened layer of the adhesive. The requirements for the aforementioned charging characteristics (half-life of static voltage) required under the conditions are arbitrary.

Examples of the particulate hydrophilicity-imparting agent include metal-based particles composed of a metal or an alloy such as Au, Ag, Ni, or Cr, and a granular body obtained by forming a metal or an alloy on the surface thereof with a substance other than a metal or an alloy as a core. a particle composed of a metal-containing compound such as a metal oxide; and a particle composed of a non-metal-based conductive compound such as graphite. Among them, particles composed of a metal oxide are preferred from the viewpoint of excellent optical properties. Here, the "metal oxide" in the present embodiment means a compound containing a metal element and oxygen, and when the metal element and the oxygen are not in a stoichiometric composition, the metal oxide such as a chemical quantity composition is also included. Doping other elements or compounds, etc. Also, it can be a composite of various types of oxides. The oxide (complex oxide), which constitutes the oxide of the multiple oxide, may also contain a non-metal oxide.

Specific examples of the particulate hydrophilicity-imparting agent composed of a metal oxide in the present embodiment include tin-doped indium oxide (ITO) powder, gallium-doped zinc oxide (GZO) powder, and cerium-doped oxidation. Tin powder, a double oxide composed of zinc oxide and ruthenium pentoxide, and a tin oxide powder doped with phosphoric acid. Among these, the conductive fine particles made of a metal oxide in the present embodiment preferably contain a complex oxide composed of zinc oxide and ruthenium pentoxide, tin oxide doped with phosphoric acid, and indium oxide doped with tin. One or two or more selected from the group are preferred.

The upper limit of the particle diameter of the particulate hydrophilicity imparting agent of the present embodiment is not particularly limited. From the viewpoint of maintaining the surface properties (particularly surface roughness) of the adhesive layer composed of the energy ray-curable hydrophilic adhesive composition, the average particle diameter is preferably 1000 nm or less, more preferably 500 nm or less, and 100 nm or less. Especially good.

The lower limit of the particle diameter of the particulate hydrophilicity-imparting agent of the present embodiment is not particularly limited. If the particle size is too small, it is difficult to suppress aggregation and maintain good dispersibility, and there is a concern that quality is uneven or productivity is low. From the viewpoint of avoiding such problems, the average particle diameter of the particulate hydrophilicity imparting agent of the present embodiment is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more.

In the energy ray-curable hydrophilic adhesive composition of the present embodiment, the content of the particulate hydrophilicity-imparting agent should be considered to be obtained by stereo-forming the hydrophilic adhesive composition of the present embodiment. The degree of hydrophilicity, the hydrophilicity imparting ability of the particulate hydrophilicity imparting agent itself, and the shape of the structural body to be obtained by three-dimensional forming (in other words, due to three-dimensional forming) The degree of deformation is equal to or equal to the setting. When the content is too small, the surface of the structure after the three-dimensional forming is difficult to obtain the desired hydrophilicity. When the content is too large, the three-dimensional formability is lowered, and the mechanical properties of the obtained structure are lowered. In the energy ray-curable hydrophilic adhesive composition of the present embodiment, the content of the particulate hydrophilicity-imparting agent is preferably a case where the particulate hydrophilicity-imparting agent is composed of tin oxide doped with phosphoric acid. The content is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and more preferably 15 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the energy ray-curable resin.

In addition, when the energy ray-curable hydrophilic adhesive composition of the present embodiment is obtained by mixing the particulate hydrophilicity-imparting agent and the energy ray-curable resin, the particulate material in the hydrophilic adhesive composition obtained is improved. In view of the dispersibility of the hydrophilicity-imparting agent, the sol obtained by dispersing a powder of a metal oxide in a liquid is preferably used as the particulate hydrophilicity-imparting agent of the present embodiment.

[adhesive sheet]

As shown in Fig. 1, the adhesive sheet 1A including the layer formed of the energy ray-curable hydrophilic adhesive composition of the present embodiment is peeled off from the peeling sheet 12 and laminated on the peeling sheet 12 in order from bottom to top. The surface of the adhesive layer 11 and the substrate 13 laminated on the adhesive layer 11 are formed.

Further, as shown in Fig. 2, the adhesive sheet 1B including the layer formed of the energy ray-curable hydrophilic adhesive composition of the present embodiment is composed of two peeling sheets 12a and 12b and two sheets in contact with each other. The adhesive layer 11 of the two peeling sheets 12a, 12b is sandwiched by the peeling surface of the peeling sheets 12a, 12b Composition. In the present specification, the peeling surface of the peeling sheet refers to a surface having peeling property in the peeling sheet, and also includes a surface on which the peeling treatment has been applied, and a surface which exhibits peeling property even if no peeling treatment is applied. One.

The adhesive layer 11 in any of the adhesive sheets 1A, 1B is formed by forming the energy ray-curable hydrophilic adhesive composition into a sheet shape. The thickness of the adhesive layer 11 can be appropriately determined depending on the molding method of the adhesive sheet 1, and the like, and is usually 1 to 300 μm, preferably 5 to 100 μm, and particularly preferably 10 to 50 μm.

The substrate 13 is not particularly limited and can be generally used as a substrate sheet for an adhesive sheet. For example, a polyester film such as polyethylene terephthalate, polybutylene phthalate or polyethylene naphthalate, a cellulose film such as triethylene fluorenyl cellulose, or a polyurethane. Film, polyethylene film, polypropylene film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, a plastic film such as a decene-based resin film or a cycloolefin resin film; a foam such as a urethane foam or a polyethylene foam; a paper such as high-quality paper, cellophane, impregnated paper, or coated paper; aluminum; A metal foil such as copper; a woven fabric or a non-woven fabric using fibers such as enamel, acryl, or polyester; and two or more laminates. It can also be a uniaxially stretched or biaxially stretched plastic film. Further, when the adhesive layer 11 is formed into a three-dimensional shape together with the base material 13, the base material 13 is preferably soft to the extent that it can be three-dimensionally formed.

The thickness of the substrate 13 is not particularly limited depending on the kind of the material or the purpose of the adhesive sheet 1, and is usually 10 to 300 μm, preferably 20 to 150 μm, and particularly preferably 35 to 80 μm.

As the peeling sheets 12, 12a, 12b, for example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a poly Vinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene - Vinyl acetate film, ionic polymer-resin film, ethylene. (Meth)acrylic copolymer film, ethylene. A (meth) acrylate copolymer film, a polystyrene film, a polycarbonate film, a polyimide film, a fluororesin film, or the like. Further, these crosslinked films can also be used. Furthermore, these laminated films are also possible.

It is preferable that the peeling surface of the peeling sheet (particularly the surface contacting the adhesive layer 11) is preferably subjected to a peeling treatment. The release agent used for the peeling treatment is, for example, an alkyd type, an anthrone type, a fluorine type, an unsaturated polyester type, a polyolefin type, or a wax type release agent.

As the adhesive sheet 1B as described above, in the case where two peeling sheets 12a, 12b are used, the materials of the two peeling sheets 12a, 12b may be the same or different, but it is preferably adjusted so that the peeling sheet 12a and the peeling sheet 12b The peeling force difference between the two is different, that is, one of them is a heavy peeling peeling sheet, and the other is a light peeling peeling sheet.

The thickness of the peeling sheets 12, 12a, 12b is not particularly limited and is usually about 20 to 150 μm.

[Manufacturing method of adhesive sheet]

The method of manufacturing the above-mentioned adhesive sheet 1A is arbitrary. As an example, a coating solution containing the energy ray-curable hydrophilic adhesive composition is applied onto a release surface of the release sheet 12, and dried to form an adhesive layer 11, and then the adhesive layer 11 is laminated. Material 13.

Further, the method of manufacturing the above-mentioned adhesive sheet 1B is arbitrary. As an example, the peeling surface of one of the peeling sheets 12a (or 12b) is coated with the above energy. The coating solution of the strand curing type hydrophilic adhesive composition is dried to form the adhesive layer 11, and the peeling surface of the other peeling sheet 12b (or 12a) is superposed on the adhesive layer 11.

The method of applying the above coating solution can be, for example, a bar coating method, a knife coating method, a roll coating method, a knife coating method, a die coating method, a gravure coating method, or the like.

The embodiments described above are described in order to facilitate the understanding of the present invention and are not intended to limit the invention. Therefore, each element disclosed in the above embodiments includes all design changes or equivalents falling within the technical scope of the present invention.

For example, the peeling sheet 12 of the adhesive sheet 1A may be omitted, or any of the peeling sheets 12a, 12b in the adhesive sheet 1B may be omitted.

[Three-dimensional forming]

As described above, in the present embodiment, the "three-dimensional forming" is a method of creating a shape in which a workpiece (the energy ray-curable hydrophilic adhesive composition or the adhesive layer 11 composed thereof) is formed in three dimensions to form a predetermined shape. . Specific examples of three-dimensionally elongating the object to be processed include a method in which a fluid or a solid having a predetermined kinetic energy is brought into contact with a processing target (a specific example of blow molding and press molding), and a raw material composition is held by a plurality of holding members and A method of relatively changing the holding position (partial stretch forming or twist forming is a specific example).

The energy ray-curable hydrophilic adhesive composition of the present embodiment and the pressure-sensitive adhesive layer 11 obtained by forming the energy ray-curable hydrophilic adhesive composition into a sheet form have a high degree of coping ability. The three-dimensional elongation has a high elongation at break and a sufficient stress relaxation rate which can stably maintain the shape of the creation after solidification until the energy line is hardened. Therefore, it is particularly suitable for three-dimensional molding.

Further, since it has excellent adhesion even before the energy ray is cured, the following molding process can be carried out: the hydrophilic adhesive composition or the adhesive layer 11 of the present embodiment (hereinafter collectively referred to as "in the description" The adhesive layer") is attached to the base, and a part of the interface between the adhesive layer and the base is supplied with gas from a surface opposite to the adhesive layer in the base, and the gas supplied thereby elongates a part of the adhesive layer From the base, a structure having a hollow portion formed by the adhesive interface between the base, the base and the adhesive layer, and the stretched adhesive layer is formed. If the energy ray hardening is performed in this state, the stretched adhesive layer surrounding the hollow portion is hardened, so that the adhesive strength of the adhesive interface between the base and the adhesive layer is lowered, and the hardened adhesive layer (adhesive hardened) can be easily hardened. The layer is constructed and has sufficient strength to be removed from the abutment. In the present embodiment, the three-dimensional molding by this method may be referred to as "elongation molding".

Further, a specific example of a method of three-dimensionally elongating the adhesive layer by elongation molding may be a method of supplying a gas (gas injection method) to the interface between the adhesive layer and the base as described above, but other methods may be used. The method extends the adhesive layer in three dimensions. Such a method is, for example, a method including a foaming agent, a method in which the protrusion is pressed upward, a method of expanding under pressure, and the like. Further, the shape of the elongation molding is not particularly limited, and examples thereof include a spherical shape, a hemispherical shape, and a columnar shape, and a continuous uneven structure may be used.

In particular, by forming the shape of the micro flow path as shown in Fig. 3, it can be used as a microreactor, and an inflow portion or a confluent portion can be provided as needed. When the method for producing a hydrophilic solid structure which is a microreactor as shown in FIG. 3 is briefly described, the adhesive layer 11 of the adhesive sheet 1 of the present embodiment is attached to a groove having a shape corresponding to a minute flow path. Abutment 21 of the surface of portion 21a (figure 3(a)) of the surface. The gap portion between the base 21 and the adhesive layer 11 formed as a result, that is, the groove portion 21a, is supplied with gas from the end opening 22a of the gas supply pipe 22 through which the groove portion 21a communicates (Fig. 3(b) ). The adhesive layer 11 on the groove portion 21a is stretched by the supplied gas, and partially swelled on the opposite side of the adhesive layer 11 from the base 21 (Fig. 3(c)). By irradiating the energy ray such as ultraviolet rays in this state, the energy ray-curable hydrophilic adhesive composition to be the adhesive layer 11 is cured. By peeling the cured product from the base 21, a hydrophilic solid structure 23 which is a microreactor can be obtained (Fig. 3(d)). As described above, when the adhesive sheet 1 of the present embodiment is used, it is possible to use elongation molding, and in particular, to manufacture a microreactor provided with an inflow portion or a confluent portion.

The energy ray-curable hydrophilic adhesive composition of the present embodiment is a composition in which the composition constitutes the adhesive layer 11 from the viewpoint of easy creation by the shape of the elongation molding, and is measured in accordance with JIS Z0237 under the following measurement conditions. The adhesive force of the adhesive layer 11 is preferably 5 N/25 mm or more before hardening and preferably 1 N/25 mm or less after hardening. This adhesion is preferably 9 N/25 mm or more before hardening and 0.5 N/25 mm or less after hardening.

Adhesive sheet: an adhesive layer 11 having a thickness of 20 μm is formed on a film composed of polyethylene terephthalate having a thickness of 25 μm.

Adhesive body: stainless steel plate, SUS304#360

Attachment time: 24 hours (placed at 23 ° C, 50% RH)

In order to illuminate the energy line irradiated by the three-dimensionally formed adhesive layer, energy lines generated from various energy ray generating devices can be used, and ultraviolet rays, electron beams, and the like are usually used. For example, ultraviolet light usually uses ultraviolet rays radiated from an ultraviolet lamp. As the ultraviolet lamp, a high-pressure mercury lamp, a FUSION H lamp, a xenon lamp or the like which emits ultraviolet light having a spectral distribution in a wavelength range of 300 to 400 nm can be used, and an irradiation amount of usually 50 to 3000 mJ/cm ² is preferable. Further, in the case of an electron beam, the irradiation amount is preferably about 10 to 1000 krad.

[Examples]

Hereinafter, the present invention will be specifically described by way of Examples and the like, but the scope of the present invention is not limited to the Examples and the like.

[Example 1] (1) Preparation of a hydrophilic adhesive composition

An acrylate copolymer obtained by copolymerizing 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid as a (meth) acrylate copolymer (weight average molecular weight: 650,000, ethyl acetate/toluene mixed solvent, glass transition temperature - 45 °C, solid content concentration: 26% by mass) 100 parts by mass (solid content), and energy ray-curable urethane acrylate oligomer (manufactured by Nippon Synthetic Chemical Co., Ltd., UV-6100B, weight average molecular weight: 6,700, glass) Transfer temperature: 0 ° C, pencil hardness after hardening 5 B) 100 parts by mass (solid content), and isocyanate-based crosslinking agent (manufactured by Nippon Polyurethane Co., Ltd., CORONATE L, solid content concentration: 75 mass%) 0.05 parts by mass ( Solid component), and 1-hydroxy-cyclohexyl-phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator, 3.0 parts by mass (the above is an energy ray-curable resin component), and as a particulate hydrophilic An energy-curable hydrophilic adhesive composition was prepared by mixing 30 parts by mass of a conductive tin oxide sol (CELNAX CX-S303IP, manufactured by Nissan Chemical Industries, Inc., average particle diameter: 5 to 20 nm).

(2) Production of adhesive sheets

The energy ray-curable hydrophilic adhesive composition prepared in the above (1) is applied to a heavy release type obtained by peeling off a single side of a polyethylene terephthalate film with an anthrone-based release agent. The release-treated surface of the sheet (SP-PET38T103-1, thickness: 38 μm, manufactured by LINTEC Co., Ltd.) was peeled off to a thickness of 20 μm, and dried at 110 ° C for 2 minutes to form two types of adhesive layers having different thicknesses. Each of the obtained adhesive layers was attached to a single side of a polyethylene terephthalate film and subjected to a release treatment by a ketone-based release agent, and a light-peelable release sheet (manufactured by LINTEC Co., Ltd., SP-) The peeling-treated surface of PET381031 and thickness 38 μm was in the form in which the adhesive layer was sandwiched between two peeling sheets. Thereafter, the mixture was aged for 7 days under conditions of 23 ° C and 50% RH to prepare an adhesive sheet. Further, in order to evaluate the haze and the total light transmittance, a dry film thickness of 5 μm was also produced.

[Embodiment 2]

The (meth) acrylate copolymer contained in the energy ray-curable hydrophilic adhesive composition of Example 1 was changed to 52 parts by mass of butyl acrylate, 20 parts by mass of methyl methacrylate, and 2-hydroxyethyl acrylate. 28 parts by mass of a copolymer (meth) acrylate copolymer (addition of 90 equivalents of methacryloxyethyl isocyanate (MOI) to 100 equivalents of hydroxyl groups of the (meth) acrylate copolymer and reacting, An adhesive sheet was produced in the same manner as in Example 1 except that the weight average molecular weight was 580,000, the ethyl acetate/toluene mixed solvent, the glass transition temperature of the MOI before the reaction was -22 ° C, and the solid content concentration was 35 mass%, 100 parts by mass. sheet.

[Example 3]

In the same manner as in Example 2, except that the particulate hydrophilicity-imparting agent of Example 1 was changed to 20 parts by mass of zinc phthalate (CELNAX CX-Z210IP, manufactured by Nissan Chemical Industries, Ltd., average particle diameter: 5 to 30 nm). Make sticky sheets.

[Example 4]

An adhesive sheet was produced in the same manner as in Example 2 except that the particulate hydrophilicity imparting agent of Example 1 was changed to 40 parts by mass of indium tin oxide (ITO) powder (manufactured by Mitsubishi Materials, Ltd., average particle diameter: 30 nm). sheet.

[Comparative Example 1]

An adhesive sheet was produced in the same manner as in Example 2 except that the particulate hydrophilicity imparting agent of Example 1 was replaced with 10 parts by mass of an ionic liquid (tetra-n-octylphosphonium bromide) as a hydrophilicity-imparting agent.

[Comparative Example 2]

The (meth) acrylate copolymer in the energy ray-curable conductive adhesive composition of Example 2 was changed to 30 parts by mass (solid content) of an acrylic resin (DIANAL BR-115, manufactured by Mitsubishi Rayon Co., Ltd.), and The energy ray-hardening urethane acrylate-based oligomer was replaced with 100 parts by mass (solid content) of dihydrocyclopentaethyl acrylate (DCPA). An adhesive sheet was produced in the same manner as in Example 2 except for the above changes.

[Comparative Example 3]

An adhesive sheet was produced in the same manner as in Example 1 except that the particulate hydrophilicity imparting agent in the composition of the energy ray-curable hydrophilic adhesive composition of Example 1 was not contained.

[Test Example 1] (Measurement of elongation at break)

The above-mentioned adhesive layer having a thickness of 20 μm is laminated, so that the total thickness of the adhesive layer in the adhesive sheet obtained in the embodiment or the comparative example becomes 500 μm, and only the peeling sheet of the outermost layer of the laminate is retained, and Placed in a 23 ° C, 50% RH gas atmosphere for 2 weeks. After that, the adhesion of the above-mentioned adhesive layers from several layers has been laminated. The sheet was cut out of a sample having a width of 15 mm and a length of 55 mm, and the peeled sheet laminated on the outermost layer of the laminate was peeled off, and the sample was placed in a universal tensile tester (Autograph AG-10kNIS, manufactured by Shimadzu Corporation). The measurement range is 15 mm wide by 25 mm long. Further, the sample was stretched at a stretching speed of 200 mm/min in an environment of 23 ° C and 50% RH, and the elongation at break of the sample was taken as the elongation at break. The results are shown in Table 1.

[Test Example 2] (Measurement of stress relaxation rate)

The above-mentioned adhesive layer having a thickness of 20 μm is laminated, so that the total thickness of the adhesive layer in the adhesive sheet obtained in the embodiment or the comparative example becomes 500 μm, and only the peeling sheet of the outermost layer of the laminate is retained, and Placed in a 23 ° C, 50% RH gas atmosphere for 2 weeks. Thereafter, a sample having a width of 15 mm and a length of 55 mm was cut out from the adhesive sheet on which the above-mentioned adhesive layer was laminated, and the peeled sheet laminated on the outermost layer of the laminate was peeled off, and the sample was placed in a universal tensile test. The machine (Autograph AG-10kNIS, manufactured by Shimadzu Corporation) has a measurement range of 15 mm wide by 25 mm long. Further, the sample was allowed to stand at a tensile speed of 200 mm/min to 300% at 23 ° C and a temperature of 50 RH, and the stress A (Pa) at the time of elongation stop and the stress B after 300 seconds from the stop of elongation were measured ( Pa). From the measured stress A and stress B, the stress relaxation rate (%) was calculated using the following formula. The results are shown in Table 1.

Stress relaxation rate (%) = {(A-B) / A} × 100 (%)

[Test Example 3] (half-life measurement)

The light-peeled sheet of the adhesive sheet having a thickness of 20 μm obtained in the adhesive layer obtained in the example or the comparative example was peeled off, and a polyester film (manufactured by Toray Industries, Inc., Lumirror) having a thickness of 38 μm was laminated on the exposed adhesive layer. A sample for half-life determination. The obtained half-life measurement sample was irradiated with a UV irradiation device (manufactured by FUSION Co., Ltd.). CV-110O-G was irradiated with ultraviolet rays (illuminance: 120 mW, light amount: 70 mJ) to harden the adhesive layer, and the obtained adhesive sheet having the adhesive hardened layer was allowed to stand in an environment of 23 ° C and 50% RH for one day. Next, the heavy peeling sheet was peeled off in the same environment, and the half-life of the static voltage of the adhesive layer after hardening was measured in accordance with JIS LT094:1997 using a charge decay measuring device (SHISHIDO-ESD, STATIC HONE STMETER Type S-5109). The results are shown in Table 1. Further, Table 1 also shows the maximum value of the static voltage of the adhesive hardened layer measured when the half-life of the static voltage was measured by the above method.

[Test Example 4] (Haze measurement)

The adhesive sheet having a thickness of 5 μm obtained in the adhesive layer obtained in the example or the comparative example was sampled in a size of 50 mm × 50 mm. The haze was measured in accordance with JIS K7136:2000 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Co., Ltd.) for removing the adhesive layer from the adhesive sheet. The results are shown in Table 1.

[Test Example 5] (Measurement of total light transmittance)

The adhesive sheet having a thickness of 5 μm obtained in the adhesive layer obtained in the example or the comparative example was sampled in a size of 50 mm × 50 mm. The total light transmittance was measured in accordance with JIS K7361:1997 using a haze meter (NDH-2000, manufactured by Nippon Denshoku Co., Ltd.) for removing the adhesive layer from the adhesive sheet. The results are shown in Table 1.

[Test Example 6] (Evaluation of elongation formability)

For the adhesive sheet obtained in the examples or the comparative examples, as shown in Fig. 4, the evaluation of the elongation formability was carried out. Specifically, the light-peelable peeling sheet 12a of the adhesive sheet 1B is peeled off (Fig. 4 (a)), and a micro syringe 14 made of stainless steel (SUS 304) (manufactured by HAMITON Co., Ltd., capacity 5 μl, type 95RN, needle) 22S PT-3) needle The tip is pressed against the exposed adhesive layer 11 (Fig. 4(b)). Then, the heavy peeling release sheet 12b was peeled off, and the needle tip of the micro syringe 14 was buried until the thickness of the adhesive layer 11 was 10 μm (Fig. 4(c)).

Then, using the micro syringe 14, 4 μl of air was injected from the tip to the adhesive layer 11, and the adhesive layer 11 was deformed only at the portion where the needle tip was buried (Fig. 4 (d)). Thereafter, the ultraviolet ray irradiation device 15 (CV-1100-G, manufactured by FUSION Co., Ltd.) was irradiated with ultraviolet rays (illuminance: 120 mW, light amount: 70 mJ) (Fig. 4 (e)), and the obtained adhesive hardened layer 11 was removed from the needle tip (Fig. 4). (f)). The resin shape of the deformed portion of the adhesive hardened layer 11 was observed, and the results are shown in Table 1. The evaluation criteria of the observed resin shape are as follows.

A: The shape of the resin is substantially spherical.

B: The shape of the resin is not expanded to a hemisphere or more, or wrinkles occur before swelling into a hemisphere.

C: The resin is not swollen and the shape is not uniform. Or damage occurs when the needle is removed, or peeled off from the needle tip before inflating.

The results are shown in Table 1.

[Test Example 7] (adhesion measurement)

An adhesive sheet having a thickness of 20 μm in the adhesive layer obtained in the example or the comparative example, and a polyester film (manufactured by Toray Industries, Inc., Lumirror) having a thickness of 25 μm laminated on the adhesive layer exposed by peeling off the lightly peeled sheet. Adhesive sheets for adhesion measurement were prepared.

Next, a size of 25 mm × 300 mm was sampled, and a roller weighing 2 kg was rubbed back and forth once on the surface of the adhesive layer exposed by peeling off the heavy peeling sheet to be adhered separately. The body (stainless steel plate, SUS304 #360) was placed in an environment of 23 ° C and 50% RH for 24 hours.

Thereafter, a tensile tester (TENSILON, manufactured by ORIENTEC Co., Ltd.) was used in the same environment, and the value (N/25 mm) measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180° was used as the adhesive force before curing.

Further, as described above, the surface of the adhesive layer was attached to the adherend and left for 24 hours, and then irradiated with ultraviolet rays (illuminance: 120 mW, light amount: 70 mJ) by an ultraviolet irradiation device (CV-110O-G, manufactured by FUSION Co., Ltd.). The value (N/25 mm) measured under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180° was used as a tacky force after hardening using a tensile tester (manufactured by OISTENTEC Co., Ltd., TENSILON).

[Test Example 8] (Ion dissolution test)

The ion elution test unit 30 shown in Fig. 5 was produced, and an ion elution test was performed.

First, an adhesive sheet having a thickness of 20 μm obtained from the adhesive layer of the embodiment or the comparative example was peeled off from the lightly peeled sheet, and the exposed adhesive layer 31 was attached to the surface to be provided with indium tin oxide by evaporation. The surface of the (ITO) layer 32 of the polyethylene terephthalate (PET) film 33 on the ITO layer 32 side. Next, the adhesive layer 31 was irradiated with ultraviolet rays (illuminance: 120 mW, light amount: 70 mJ) from the side of the adhesive sheet 31 using an ultraviolet irradiation device (manufactured by FUSION Co., Ltd., CV-110O-G), and the laminate was hardened by sequential lamination. The adhesive sheet 31, the ITO layer 32, and the electrode sheet 34 for the PET film 33.

Further, one sheet for the electrode 34 is prepared. As shown in FIG. 5, the electrode sheets 34 are disposed such that the ITO layer 32 of the adhesive layer 31 after hardening is opposite. The side surfaces were opposed to each other with a gap 35 of 50 μm therebetween, and the ion elution test unit 30 was obtained.

The oxime oil (KF-96, manufactured by Shin-Etsu Chemical Co., Ltd.) was filled in a gap 35 of 50 μm of the ion elution test unit 30 in an environment of 23 ° C and 50% RH.

The ITO layer 32 of the PET layer 33 and the surface on the opposite side were used as the electrodes of the ion elution test unit 30, and a constant voltage (15 kV) was applied to these surfaces, and a voltage of 60 seconds was applied after the voltage application, and voltage application was started. The comparison system hardly considers a change in current value (A) or an increase in current value (F) to evaluate whether ions are easily eluted from the adhesive layer 31 after hardening to the fluorenone oil.

A: I almost don't think the current value changes.

F: Confirm the increase of current value

As is clear from Table 1, the energy ray-curable hydrophilic adhesive composition obtained by the examples satisfying the requirements of the present invention is excellent in three-dimensional formability, and the cured product of the composition includes sufficient hydrophilicity.

[Industry Utilization]

The energy ray-curable hydrophilic adhesive composition and the adhesive sheet of the present invention are three-dimensionally formed and further energy-hardened to form a hydrophilic structure, which is suitable for applications requiring hydrophilicity such as a microreactor. .

1A‧‧‧Adhesive sheets

11‧‧‧Adhesive layer

12‧‧‧ peeling sheet

13‧‧‧Substrate

Claims (14)

An energy ray-curable hydrophilic adhesive composition comprising an energy ray-curable resin and a particulate hydrophilicity-imparting agent dispersed in the energy ray-curable resin, characterized in that the energy ray-curable hydrophilic adhesive The elongation at break of the composition before the energy ray hardening is 2000% or more, and the stress relaxation rate is 70% or more and 95% or less, and the average particle diameter of the particulate hydrophilicity-imparting agent is 1000 nm or less, and the energy ray-curable hydrophilicity is used. When the adhesive composition is formed into a 20 μm thick adhesive layer formed on a polyethylene terephthalate resin sheet having a thickness of 38 μm, and the adhesive layer is subjected to energy ray hardening to obtain an adhesive hardened layer. The half-life of the static voltage measured by the half life measuring machine defined by JIS L1094:1997 is 25 ° C, 50% RH is 60 seconds or less, wherein the energy ray-hardening resin contains (meth) acrylate copolymer and energy ray hardening type. Urethane acrylate. The energy ray-curable hydrophilic adhesive composition according to claim 1, wherein the particulate hydrophilicity-imparting agent is composed of a metal oxide. The energy ray-curable hydrophilic adhesive composition according to claim 1, wherein the metal oxide contains a group selected from the group consisting of tin oxide doped with phosphoric acid and complex oxide composed of zinc oxide and antimony pentoxide. One or two or more of the groups. The energy ray-curable hydrophilic adhesive composition according to claim 1, wherein when the energy ray-curable hydrophilic adhesive composition is made of a 5 μm thick adhesive layer, the total light is worn before the energy ray hardening. Transmittance 80% or more, and the adhesive layer has a haze of 10% or less. The energy ray-curable hydrophilic adhesive composition according to claim 1, wherein the energy ray-curable urethane acrylate is 50 parts by mass based on 100 parts by mass of the (meth) acrylate copolymer. ~200 parts by mass. The energy ray-curable hydrophilic adhesive composition of claim 1, wherein the (meth) acrylate copolymer has a glass transition temperature (Tg) before the energy ray hardening is -50 to 0 ° C, and The energy transfer line of the energy ray-hardening urethane acrylate has a glass transition temperature (Tg) of -40 to 20 °C. The energy ray-curable hydrophilic adhesive composition according to claim 1, wherein the energy hardening of the energy ray-curing urethane acrylate has a pencil hardness of B to 5B. The energy ray-curable hydrophilic adhesive composition of claim 1, which is used for stereoscopic molding. The energy ray-curable hydrophilic adhesive composition according to claim 8, wherein the energy ray-curable hydrophilic adhesive composition is three-dimensionally formed by three-dimensional elongation. An adhesive sheet comprising: an adhesive layer comprising the energy ray-curable hydrophilic adhesive composition according to any one of claims 1 to 9. An adhesive sheet comprising: an adhesive layer composed of the energy ray-curable hydrophilic adhesive composition according to any one of claims 1 to 9; and 2 for holding the adhesive layer The sheet is peeled off. a hydrophilic construct characterized by: The energy ray-curable hydrophilic adhesive composition according to any one of the items 1 to 9 is obtained by three-dimensionally elongating and three-dimensionally forming. A hydrophilic structure obtained by three-dimensionally stretching an adhesive layer in an adhesive sheet according to claim 10 of the patent application. A hydrophilic structure obtained by three-dimensionally stretching an adhesive layer in an adhesive sheet according to claim 11 of the patent application.