JP2009134255A - Micropattern forming material, micropattern complex material and method for producing the same, and method for producing minute three-dimensional structure substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a micropattern forming material which facilitates alignment of each layer and achieves reliable adhesion, with respect to a micropattern complex material having a plurality of micropattern members of ≤10 μm size for forming minute cell structures such as flow passages in a layer stack. <P>SOLUTION: The micropattern forming material for forming a micropattern member 5A cures partially by being partially provided with a first trigger, and after removal of a part other than the partially cured part, the material cures and develops adhesive properties by being provided with a second trigger different from the first trigger. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a material for forming a micropattern used for manufacturing, for example, a microchip used for downsizing a chemical experiment or analyzing a small amount of specimen. More specifically, the present invention relates to a micrometer. The present invention relates to a micropattern forming material, a micropattern composite material, a manufacturing method thereof, and a manufacturing method of a micro three-dimensional structure substrate for obtaining a micropattern member having a through portion or a groove of an order or less.

  A micro-chip type liquid manipulation device called Lab-on-a-Chip or micro-TAS, micro-chemical chip, etc., capable of manipulating a minute volume of fluid by a micro structure including a micro cavity and a micro channel having a capillary size of 1 μm to 1 mm. It has been known. Such devices are attracting attention as equipment for downsizing chemical experiments, or for performing analysis easily and quickly at the site of specimen generation.

  This type of device has a laminate including at least two or more substrates. A microchannel is formed on a part of one side and / or the other side of the substrate. In order to perform component analysis or synthesis in the minute channel, gas or liquid is introduced to perform analysis or reaction.

  In order to reduce the cost of the device such as a microchip, a substrate made of plastic is used. However, as the microchannels become even smaller, it becomes difficult to bond the substrates without filling the microchannels.

  The following Patent Document 1 discloses a photosensitive resin composition comprising (A) a compound having a ring-opening polymerizable reactive group in the molecule and (C) a compound that absorbs high energy rays and generates an acid or a base as essential components. Is disclosed. By irradiating the entire surface of the photosensitive resin composition with high energy rays, the composition becomes semi-cured. Next, a part of the semi-cured composition is removed by irradiation with laser light. By passing through these steps, a three-dimensional pattern having a fine flow path is obtained.

On the other hand, Patent Document 2 below discloses a method for producing a microreactor using a resist film made of a photo post-curing resin composition. According to this method, it is possible to manufacture a microreactor in which substrates on which fine channels are accurately formed are accurately stacked without causing distortion or the like.
JP 2003-307849 A JP 2005-329479 A

  In the method for producing the photosensitive resin composition described in Patent Document 1 and the microreactor described in Patent Document 2, a micropattern member such as a three-dimensional pattern or a substrate in which fine channels are formed can be obtained. Moreover, since the produced micropattern member maintains adhesiveness, the micropattern member can be laminated on another member, or the micropattern members can be laminated and bonded. However, if the flow path width is less than 10 μm, the mass productivity of the micropattern member in which the fine flow path is accurately formed deteriorates. Moreover, since the member after micro pattern formation has adhesiveness, it was not possible to use a contact alignment method, that is, a method of performing accurate positioning while recontacting many times. Therefore, workability is low when precise positioning between members is required.

  An object of the present invention is to form a micropattern for forming a micropattern that has a fine structure with a minimum width of 10 μm or less and can be applied with a contact alignment method for precise alignment in view of the current state of the prior art described above. It is in providing the manufacturing material, the micro pattern composite material, its manufacturing method, and the manufacturing method of a micro three-dimensional structure board | substrate. A more specific object of the present invention is to provide a micropattern composite material having a delayed adhesive micropattern caused by near-ultraviolet light stimulation, in particular, which does not require heating during bonding.

  The material for forming a micropattern according to the present invention is a material for forming a micropattern for forming a micropattern member. The material for forming a micropattern is partially cured by being partially provided with a first trigger, and is partially After a portion other than the cured portion is removed, a second trigger different from the first trigger is applied to cure and develop adhesiveness.

  On the specific situation with the micropattern formation material which concerns on this invention, a said 1st trigger is light and a said 2nd trigger is light. In this case, since both the first and second triggers are light, it is suitably used for manufacturing a micropattern member in which heating is not preferable. In addition, since no heating device is required, the manufacturing equipment can be simplified.

  The material for forming a micropattern according to the present invention is preferably an alkali-soluble binder resin (A), a radical polymerizable compound (B), a photo radical generator (C), and an ion polymerizable resin (D). A composition containing a photoion polymerization catalyst (E) is used. In this case, for example, irradiation with light for activating the photoradical generator (C) as the first trigger is performed, and irradiation with light for activating the photoion polymerization catalyst (E) is performed as the second trigger. By doing so, a micropattern member can be obtained.

  More preferably, P2 / P1, which is the ratio of the total applied amount (P2) of the second trigger to the total applied amount (P1) of the first trigger, is in the range of 1-100. In this case, patterning can be performed satisfactorily by applying the first trigger, and sufficient adhesiveness can be expressed by applying the second trigger.

  In a specific aspect of the material for forming a micropattern according to the present invention, the first trigger is light and the second trigger is heat. Thus, when the first trigger is light, heat may be used as the second trigger. In that case, preferably, as a material for forming a micropattern, an alkali-soluble binder resin (A), a radical polymerizable compound (B), a photo radical generator (C), and an ion polymerizable resin (D) A composition containing a thermosetting agent (F) is preferably used.

  A micropattern composite material according to the present invention includes a support and a micropattern member formed on the support and constituting a micropattern, and the micropattern member is provided according to the present invention. It consists of the material obtained by providing the 1st trigger to the material for micro pattern formation, and expresses adhesiveness after the 2nd trigger is provided.

  In the micropattern composite material according to the present invention, a micropattern member having no adhesive force or having slightly adhesiveness is prepared while being supported by a support. Therefore, since the micropattern in the state supported by the support is handled and the contact alignment method can be applied, a micro three-dimensional structure described later in which a large number of micropatterns are laminated and bonded after precise alignment can be easily performed. And it can form with high precision.

  In the micropattern composite material according to the present invention, preferably, the Young's modulus in the thickness direction of the micropattern member is 1 to 5 MPa. In the case of a micropattern member having a Young's modulus in the thickness direction of 1 to 5 MPa, even when a very small three-dimensional structure such as a hollow structure, a bridge structure, or a cantilever structure is present on the adherend Adhesion can be achieved without filling these structures. Preferably, the peeling force with respect to the support before applying the second trigger of the micropattern member is 0.02 N / 10 mm or less.

  The method for producing a micropattern composite material according to the present invention includes a step of laminating a micropattern forming material configured according to the present invention on a support, and before laminating the micropattern formation material on the support, or After stacking, applying a first trigger and patterning the micropattern forming material to form a micropattern member, thereby obtaining a micropattern composite having a support and a micropattern member; Is provided.

  A method for manufacturing a micro three-dimensional structure substrate according to the present invention includes a step of laminating a micropattern forming material configured according to the present invention on a support, and laminating the micropattern forming material on the support. Forming a micropattern member by patterning a micropattern forming material by applying a first trigger, thereby obtaining a micropattern composite having a support and a micropattern member; and the micropattern member A step of applying a second trigger to the substrate and causing the micropattern member to exhibit adhesiveness, and a step of pressure-bonding the micropattern member of the micropattern composite material to the surface of the substrate.

  In a specific aspect of the method for manufacturing a micro three-dimensional structure substrate according to the present invention, the method further includes a step of peeling the support from the micro pattern member after the micro pattern member is pressure-bonded to the substrate.

  In still another specific aspect of the method for manufacturing a micro three-dimensional structure substrate according to the present invention, after the support is peeled off, a micro pattern member of a new micro pattern composite material is further pressure-bonded onto the micro pattern member. And a step of peeling a new micropattern composite support.

  According to still another specific aspect of the method for manufacturing a micro three-dimensional structure substrate according to the present invention, before the support is peeled off and the exposed micropattern member completes the adhesion reaction, the micropattern member The method further includes the step of laminating and adhering other members. As described above, a multilayered micro three-dimensional structure substrate may be obtained by performing a process of laminating and bonding other members than the micro pattern member on the micro pattern member.

  In still another specific aspect of the method for manufacturing a micro three-dimensional structure substrate according to the present invention, the second trigger is provided to the micropattern member after the micropattern member is pressure-bonded. As described above, the second trigger may be provided after the micropattern member is crimped. Therefore, the micropattern member can be easily crimped while the micropattern member is soft, and then the second trigger is provided. By imparting, the micropattern member can be cured.

  Further, depending on the composition of the micropattern forming material, a second trigger may be applied before pressure-bonding to the substrate or the like, and the adhesiveness may be delayed by delayed curing.

  Moreover, even if it is a lot of independent patterns in which the patterns of the respective layers forming the minute three-dimensional structure are not connected, they are collectively transferred and joined. Therefore, a minute three-dimensional structure substrate in which many minute three-dimensional structures are highly integrated can be manufactured stably and reliably.

  Details of the present invention will be described below.

  First, the material for forming a micropattern used for forming the micropattern in the present invention will be described.

  The micropattern forming material according to the present invention is a micropattern forming material for forming a micropattern member on a support, and is partially cured by being given a first trigger, And after removing parts other than the part hardened | cured partially, it is a micropattern formation material which hardens | cures and expresses adhesiveness by giving the 2nd trigger different from a 1st trigger.

  The first trigger and the second trigger are not particularly limited, and various active energy rays such as light and heat can be used. Preferably, a micropattern forming material in which the first trigger is light and the second trigger is light is used. In this case, the material for forming a micropattern according to the present invention can be suitably used for applications where heating is not appropriate. For example, when forming a micropattern member containing a material that is denatured by heating such as protein, it is preferable that both the first and second triggers are light.

  As the material for forming a micropattern in which the first trigger is light and the second trigger is light, an alkali-soluble binder resin (A), a radical polymerizable compound (B), and a photo radical generator A composition containing (C), an ion polymerizable resin (D), and a photoion polymerization catalyst (E) is used. In this case, light for activating the photoradical generator (C) may be irradiated as the first trigger, and light for activating the photoion polymerization catalyst (E) may be irradiated as the second trigger.

  By activating the photoradical generator (C), photoradicals are generated, whereby the polymerization of the radical polymerizable compound (B) proceeds and is semi-cured. Further, when the alkali-soluble binder resin (A) has a reactive functional group in the side chain, co-crosslinking or copolymerization of the alkali-soluble binder resin (A) and the radical polymerizable compound (B) proceeds. Semi-cured. Therefore, when the light as the first trigger is partially irradiated, the portion irradiated with the light can be semi-cured. And the patterning can be performed by treating the portion not irradiated with light with an alkali to dissolve and remove the alkali-soluble binder resin (A).

  In addition, when alkali-soluble binder resin (A) does not have a reactive functional group in a side chain, it does not harden | cure and alkali-soluble binder resin (A) has only the role as a binder.

  By providing the first trigger, a micropattern member of a micropattern composite material according to the present invention described later is obtained. This micro-pattern member is in a state before the second trigger is applied and thus before the adhesiveness is developed.

  Preferred first to third aspects of the micropattern forming material will be described.

  As the first aspect of the micropattern forming material, (A) an alkali-soluble binder resin, (B) a radical polymerizable compound, (C) a photo radical generator, (D) an ion polymerizable resin, E) a photoion polymerization catalyst, wherein the first and second triggers are light, and the ratio of the total applied energy of light as the second trigger to the total applied energy of light as the first trigger Is a material for forming a micropattern in a range of 1 to 100 times.

  In addition, the second embodiment includes (A) an alkali-soluble binder resin, (B) a radical polymerizable compound, and (C-1) a photo radical generator that generates radicals when given light having a wavelength of 400 nm or more. , (D) an ion polymerizable resin, and (E-1) an ion polymerization catalyst that is activated when irradiated with light having a wavelength of less than 400 nm, wherein the first trigger is light, and the second The trigger is light, and the wavelength of light as the first trigger is longer than the wavelength of light as the second trigger.

  Furthermore, the third aspect includes (A) an alkali-soluble binder resin, (B) a radical polymerizable compound, (C) a photo radical generator, (D) an ion polymerizable resin, and (F) the ion polymerizable resin. A material for forming a micropattern, including a thermosetting agent that cures the resin (D) by heating, wherein the first trigger is light and the second trigger is heat.

  Details of each component used in the material for forming a micropattern according to the first to third aspects will be described.

(A) Alkali-soluble binder resin:
The alkali-soluble binder resin (A) is made of an appropriate synthetic resin that can be dissolved during development with an alkali developer. Such a synthetic resin is not particularly limited as long as it is soluble in an alkali developer, but a (meth) acrylic resin synthesized so as to have a carboxyl group or a hydroxyl group which is an alkali-soluble group in the side chain, Examples thereof include polyester resins, polycarbonate resins, polyamide resins, polyimide resins, polyether resins, phenol resins, and cresol novolac resins. Moreover, you may use resin modified so that thermoplastic elastomers, such as SBS and SIS, may have alkali-soluble groups, such as a carboxyl group and a phenolic hydroxyl group. Preferably, (meth) acryl synthesized so as to have a carboxyl group or a hydroxyl group in the side chain, because it is easy to control the alkali dissolution rate, the adhesiveness, and the compatibility with other components. System resin is desirable.

  The alkali-soluble binder preferably has a reactive functional group in the side chain, and preferably has a polymerizable double bond.

  The (meth) acrylic resin synthesized so as to have a carboxyl group or a hydroxyl group in the side chain includes a (meth) acrylic acid alkyl ester compound as a copolymerizable monomer, a carboxyl group or a hydroxyl group and an unsaturated group. A (meth) acrylic copolymer obtained by copolymerizing a (meth) acrylic monofunctional compound having a double bond can be suitably used.

  Moreover, as said alkali-soluble binder resin (A), you may use the (meth) acryl copolymer which has a (meth) acryl group and a carboxyl group in a side chain. Since the (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain is co-crosslinked with the radical polymerizable compound (B), the resolution in the exposure / development process is further increased.

  Examples of the (meth) acrylic copolymer having a (meth) acrylic group and a carboxyl group in the side chain include a main chain composed of at least a structural unit having an acidic functional group and a structural unit having a hydroxyl group, and a radical. A polymer in which the polymerizable group-containing isocyanate compound has an amide bond to at least a part of the acidic functional group and / or a urethane bond to at least a part of the hydroxyl group through the isocyanate group of the isocyanate compound is preferable. is there.

  The method for copolymerizing the above copolymerizable monomer with a (meth) acrylic monofunctional compound having a carboxyl group or a hydroxyl group and an unsaturated double bond is not particularly limited. For example, a radical polymerization initiator and necessary Depending on the method, polymerization may be carried out by a conventionally known method such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization using a molecular weight regulator. Of these, solution polymerization is preferred.

  In addition, what is necessary is just to select suitably the glass transition temperature Tg and molecular weight of the said alkali-soluble binder resin (A) by the relationship with the other component combined.

  As said alkali-soluble binder resin (A), only 1 type of resin may be used and 2 or more types of resin may be used together.

  About the mixture ratio of alkali-soluble binder resin (A) in the curable composition for micropattern formation, a total of 100 weight part of alkali-soluble binder resin (A), radically polymerizable compound (B), and ion-polymerizable resin (D). The proportion is preferably 20 to 40 parts by weight. If it is less than 20 parts by weight, alkali development may not be possible, and if it exceeds 40 parts by weight, water resistance may be deteriorated. More preferably, it is 25 to 35 parts by weight.

(B) Radical polymerizable compound:
As the radical polymerizable compound (B), an appropriate compound that is polymerized by generated radicals can be used. Examples of such radical polymerizable compounds include the following b1) radical polymerizable monomer, b2 An oligomer having a radical polymerizable double bond) and / or a compound or copolymer having b3) two or more radical polymerizable double bonds in one molecule is preferably used.

b1) Radical polymerizable monomer The radical polymerizable monomer b1) is other than a compound or copolymer having two or more radical polymerizable double bonds in one molecule, that is, other than the compound or copolymer b3). It is a radical polymerizable monomer.

  As the radical polymerizable monomer, an appropriate monomer that can make the micropattern forming material semi-cured when the first trigger is applied is used. Especially, since the degree of a semi-hardened state can be controlled easily, (meth) acrylic-acid alkylester is used suitably. Such (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Hydroxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclo (meth) acrylate Examples include pentanyl and benzyl (meth) acrylate. In the present specification, (meth) acrylic acid means acrylic acid or methacrylic acid.

  Other radical polymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, and p-chlorostyrene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; From unsaturated dicarboxylic anhydrides such as maleic anhydride; aromatic substituted maleimides such as phenylmaleimide, benzylmaleimide, naphthylmaleimide, o-chlorophenylmaleimide; alkyl-substituted maleimides such as methylmaleimide, ethylmaleimide, propylmaleimide, isopropylmaleimide, etc. May be used. These may be used in place of (meth) acrylic acid ester as a radical polymerizable monomer, or may be used as a mixture.

b2) Oligomer having a radical polymerizable double bond The above b2) oligomer having a radical polymerizable double bond is not particularly limited as long as it has a radical polymerizable double bond. Examples thereof include (meth) acrylic oligomers, polyester oligomers, polycarbonate oligomers, polyamide oligomers, polyimide oligomers, polyurethane oligomers, polyether oligomers, phenol oligomers, and cresol novolac oligomers. Further, as the above oligomer, a thermoplastic elastomer such as SBS or SIS was modified so as to have a radical polymerizable double bond such as (meth) acryloyl group, styryl group, vinyl ester group, or vinyloxy group. An oligomer may be used.

  As said oligomer b2), only 1 type of oligomer may be used and 2 or more types of oligomers may be used together.

b3) Compound or copolymer having two or more radically polymerizable double bonds in one molecule As the compound or copolymer b3), as long as it has two or more radically polymerizable double bonds in one molecule, It is not particularly limited. Examples thereof include an appropriate compound having two or more functional groups having a radical polymerizable double bond in one molecule and a (meth) acrylic polymer having a radical polymerizable double bond in a side chain. Examples of such a functional group having a radical polymerizable double bond include a (meth) acryloyl group, a styryl group, a vinyl ester group, and a vinyloxy group.

  As a method for preparing a (meth) acrylic polymer having a radical polymerizable double bond in the side chain, a (meth) acrylic acid alkyl ester polymer having a hydroxyl group or a carboxyl group in the side chain, and a reaction with the hydroxyl group or the carboxyl group And a method of reacting a compound having a reactive double bond with a compound having a reactive double bond.

  Specific examples of the compound having a group that reacts with the hydroxyl group or the carboxyl group and a reactive double bond include 2-methacryloyloxyethyl isocyanate or 1,1-bis (acryloxymethyl) ethyl isocynate.

  Examples of the compound or copolymer b3) include trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, and dipentaerythritol di. A compound obtained by modifying a bifunctional (meth) acrylate compound such as (meth) acrylate with caprolactone; pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol tetra (meth) And compounds obtained by modifying caprolactone with a tri- or higher functional (meth) acrylate compound such as acrylate and dipentaerythritol penta (meth) acrylate.

  As for the said compound or copolymer b3), only 1 type may be used and 2 or more types may be used together.

  The glass transition temperature Tg of the (B) radical polymerizable compound and the molecular weight of the (B) radical polymerizable compound in the micropattern forming material may be appropriately selected depending on the relationship with other components to be combined.

  About the mixture ratio of the (B) radically polymerizable compound in the micropattern forming material, the total of 100 parts by weight of the alkali-soluble binder resin (A), the radically polymerizable compound (B) and the ionic polymerizable resin (D). 40 to 70 parts by weight. If the amount is less than 40 parts by weight, the shape corresponding to the fine pattern may not be transferred. If the amount exceeds 70 parts by weight, sufficient adhesion to the substrate may not be exhibited. More preferably, it is 50-60 weight part.

(C) Photoradical generator:
Examples of the photo radical generator (C) include an appropriate compound that is activated by light irradiation as a first trigger and generates a radical. Preferably, a photo-radical reaction initiator that is activated by light irradiation and radical-crosslinks the above-mentioned copolymerizable monomer b1), oligomer b2) and compound or copolymer b3) can be used.

  When activating the photoion polymerization catalyst (E) described later, a photo radical generator (C-1) activated by light having a wavelength different from the light used to activate the photoion polymerization catalyst (E) It is desirable to use For example, when the photoion polymerization catalyst (E) is activated by light having a wavelength shorter than 400 nm as the second trigger, the photoradical generator (C-1) is sensitized by light having a wavelength longer than 400 nm. A compound is preferably used. However, even if the excitation wavelength of the photoradical generator (C) and the excitation wavelength of the photoion polymerization catalyst (E) overlap, there is a difference between the reaction rate of the radical chain reaction and the reaction rate of the ionic polymerization reaction. It is possible to achieve both the ability to form fine patterns and the photocuring adhesiveness. In order to more clearly separate the functions of the fine patterning performance and the adhesion, it is applied to give adhesion to the total light energy P1 applied when the first trigger is given, i.e. The ratio P2 / P1 of the applied light energy total amount P2 when the second trigger is applied is preferably 1 to 100. If the ratio P2 / P1 is less than 1, photocuring adhesion failure may occur, and if it exceeds 100, a fine pattern may not be formed with high accuracy.

  Such a photoradical generator (C) is not particularly limited, and examples thereof include conventionally known photoreaction initiators such as benzoin, benzophenone, benzyl, thioxanthone, and derivatives thereof. Specifically, for example, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, Michler ketone, (4- (methylphenylthio) phenyl) failmethanone, 2,2-dimethoxy-1,2-diphenylethane-1- ON, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl) -2-hydroxy-2 -Methyl-1-propan-1-one, 2-methyl-1 (4-methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphospho Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone, 2-chloro Examples include thioxanthone. These photoinitiators may be used independently and 2 or more types may be used together.

  As the photo radical generator (C-1) activated by light having a wavelength longer than 400 nm, a bisacylphosphine oxide radical generator, specifically, bis (2,4,6-trimethylbenzoin) -phenyl Phosphine oxide (manufactured by Ciba Specialty Chemicals, trade name Irgacure 819), titanocene radical generator, specifically, bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro -3- (1H-pyrrol-1-yl) -phenyl] titanium (manufactured by Ciba Specialty Chemicals, trade name Irgacure 784) and the like.

  Further, as the photo radical generator (C-1) activated at a wavelength different from that of the photoion polymerization catalyst (E), for example, a combination of a dye and a radical generator or a hydrogen donor, or an α-diketone It is preferable to use a derivative and a hydrogen donor in combination. In addition to a single visible light polymerization initiator, organic peroxide and dye, diphenyliodonium salt and dye, imidazole and keto compound, hexaarylbiimidazole compound and hydrogen donating compound, mercaptobenzothiazole and thiopyrylium salt, metal arene A combination of a hexaarylbiimidazole such as cyanine dye and a known initiator such as a radical reaction initiator may be used.

  (C) About the mixture ratio of a photoradical generator, the range of 0.01-10 weight part is preferable with respect to a total of 100 weight part of (B) radically polymerizable compound, More preferably, it is 0.05-5. Parts by weight. If it is less than 0.01 parts by weight, the photopolymerization / polymerization of the radically polymerizable compound (B) may not proceed sufficiently, or the crosslinking / polymerization rate may be too slow. If it exceeds 10 parts by weight, There exists a possibility that the physical property of the obtained micro pattern member may fall.

(D) Ion polymerizable resin:
The ion polymerizable resin (D) is a compound that has an ionic reactive group and is cured by the reaction of the ionic reactive group by irradiation with light and / or heating. As the ionic reactive group of the ion polymerizable resin (D), an anionic functional group and a cationic functional group exist. Examples of the cation reactive group include an epoxy group, an oxetanyl group, a vinyloxy group, a styryl group, and an alkoxysilyl group.

  Examples of the anionic functional group include an epoxy group, an alkoxysilyl group, and a (meth) acryloyl group.

  As the ion-polymerizable resin (D), a compound having two or more ion-reactive functional groups such as an epoxy group, an oxetanyl group, a vinyloxy group, a stearyl group, or an alkoxysilyl group in one molecule is preferable. . More specifically, examples include various epoxy compounds that are cured by light irradiation and / or heating. Examples of such epoxy compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, epoxidized soybean oil, and epoxidized SBS. Can be mentioned.

  About the mixture ratio of the said ion polymerizable resin (D), it is 10-20 weight with respect to a total of 100 weight part of alkali-soluble binder resin (A), a radically polymerizable compound (B), and an ion polymerizable resin (D). The ratio of parts is preferred. If it is less than 10 parts by weight, sufficient cured adhesiveness to the substrate may not be obtained, and if it exceeds 20 parts by weight, the mold transfer property may be deteriorated.

(E) Photoion polymerization catalyst:
The photoionic polymerization catalyst (E) is a compound that is activated by light to generate ions and hardens the ion polymerizable resin (D) by ionic polymerization.

  The photoionic polymerization catalyst (E) is activated by light and advances the ionic polymerization reaction of the ionic polymerizable resin (D). Examples of the photoion polymerization catalyst (E) include compounds that generate cations upon irradiation with light, such as photosensitive onium salts and ferrocene compounds. Various photocationic polymerization initiators can be used as the cation-generating compound. Examples of the photocationic polymerization initiator include photosensitive onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, metallocene salts such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes, and pyridinium. Etc.

  Among the above photocationic polymerization initiators, aromatic iodonium salts and aromatic sulfonium salts do not generate cations with light outside the ultraviolet region, but are known sensitizers such as aromatic amines and polycyclic aromatic hydrocarbons. By using a sensitizer having an excitation absorption band in the visible light region in combination, cations can be generated even in light in the visible region. Further, when a metallocene salt is used, an oxalate ester of tertiary alcohol may be used as a reaction accelerator.

More, specifically, as the photosensitive onium salt, triaryl sulfonium salt, diaryl sulfonium salts, such as diaryliodonium salts ^{SbF 6-, PF 6-, BF 4-} , B (PhF 5) 4 Examples thereof include compounds having ⁻ as a counter anion. Examples of the iron-allene complex include an Fe-ferrocene complex. In addition, since the said photocationic polymerization initiator can produce | generate a cation only with the light of wavelength 400nm or less, it can be used as (E) photoionic polymerization catalyst of this invention.

  Commercially available photocationic polymerization initiators are broadly classified into ionic photoacid generation types and nonionic photoacid generation types. Examples of ionic photoacid generation type photocationic polymerization initiators include the trade name “ Adeka optomer SP150 "," Adeka optomer SP170 "(manufactured by Asahi Denka Kogyo Co., Ltd.), trade name" UVE-1014 "(manufactured by General Electronics Co., Ltd.), trade name" CD-1012 "(manufactured by Sartomer), etc. Can be mentioned.

  Examples of the nonionic photoacid generation type photocationic polymerization initiator include nitrobenzyl ester, sulfonic acid derivative, phosphoric ester, phenol sulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate, and the like.

  As for the said photoion polymerization catalyst (E), only 1 type may be used independently and 2 or more types may be used.

  About the mixture ratio of the said photoion polymerization catalyst (E), it is preferable to set it as the range of 0.1-50 weight part with respect to 100 weight part of (D) ion polymerizable resin, More preferably, it is 1-10 weight part. Range. If the amount is less than 0.1 part by weight, curing of the (D) ion-polymerizable resin is insufficient due to light irradiation, and the adhesion to the substrate may not be sufficiently increased. Moreover, when it exceeds 50 weight part, there exists a possibility that the physical property of the micropattern member obtained may fall.

(F) Thermosetting agent:
The thermosetting agent (F) accelerates the curing of the ion polymerizable resin (D) by heating. Examples of such a thermosetting agent (F) include a curing agent having an appropriate amine and / or thiol group. Hydrazide compounds such as 1,3-bis [hydrazinocarbonoethyl-5-isopropylhydantoin], dicyandiamide, guanidine derivatives, 1-cyanoethyl-2-phenylimidazole, N- [2- (2-methyl-1-imidazolyl) Ethyl] urea, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, N, N′-bis (2-methyl-1-imidazolylethyl) urea, N , N ′-(2-methyl-1-imidazolylethyl) -adipamide, 2-phenyl-4-methyl-5-hydroxymethylimidazole, imidazole derivatives such as 2-phenyl-4,5-dihydroxymethylimidazole, modified aliphatic Polyamine, tetrahydrophthalic anhydride, ethylene glycol bis (anhydro trimellitate) And the like, and addition products of various amines and epoxy resins.

  About the mixture ratio of the said thermosetting agent (F), it is preferable to set it as the range of 1-100 weight part with respect to 100 weight part of (D) ion polymerizable resin, More preferably, it is the range of 5-50 weight part. is there. If the amount is less than 1 part by weight, curing of the (D) ion polymerizable resin may be insufficient due to heating, and adhesion to the substrate may not be sufficiently increased. Moreover, when it exceeds 100 weight part, there exists a possibility that the physical property of the micro pattern member obtained may fall.

(Other ingredients)
As long as the object of the present invention is not impaired, other components may be appropriately added to the micropattern forming material. Such other components include a solvent for forming a film on the support, a plasticizer for imparting flexibility, a reaction accelerator or a reaction inhibitor for controlling photoreactivity, and appropriate filling. Agents, antioxidants for enhancing stability, ultraviolet absorbers for enhancing weather resistance, oxygen absorbers and the like. In order to impart conductivity, metal fine particles, organic conductive compounds, solid electrolytes, or the like may be added.

(light source)
As a light source for proceeding photocrosslinking and curing in the micropattern forming material, an appropriate light source can be used according to the wavelength of light to be used. Examples of such light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, excimer lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, xenon lamps, A fluorescent lamp, sunlight, an electron beam irradiation apparatus, UV-LED, etc. are mentioned. Further, unnecessary wavelength components may be reduced or removed using a filter or the like, or various light sources may be used in combination.

(Heat source)
Moreover, when using heat as a trigger for hardening of a thermosetting agent (E), an appropriate heat source can be used. Examples of such a heat source include a heater, a furnace, or an infrared light irradiation device that emits infrared light.

(Preferred physical properties of micropattern member)
The semi-cured product after the first trigger is applied to the micropattern forming material, that is, the surface tack of the micropattern member is preferably 4 to 20. If the tack is less than 4, it may slip during bonding to the substrate, making positioning difficult. On the other hand, if it exceeds 20, there is a possibility that the alignment correction becomes difficult. The tack is a value measured by the following method.

Tack measurement:
A micropattern-forming material was cast on a PET film having a thickness of 50 μm that had been subjected to a mold release treatment so as to have a thickness of 20 μm, thereby preparing a resin film. A PET film having a thickness of 50 μm was laminated as a cover film.

Before measuring the tack, the cover film surface was irradiated with UV light having a main emission wavelength of 400 nm and an illuminance of 1 mW / cm ² for 120 seconds. Next, the cover film was peeled off to expose the resin film, and a tack measurement sample was obtained. The tack was measured according to the JIS Z 0237 ball tack test.

The adhesive force with the substrate after the micropattern member of the present invention is attached to the substrate and the second trigger is applied is preferably 0.05 N / cm ² or more. If the adhesive force is less than 0.05 N / cm ² , there is a risk of peeling from the substrate, and the intended hollow structure may not be maintained. The adhesive force is a value measured by the following method.

Adhesion measurement:
A micropattern-forming material was cast on a PET film having a thickness of 50 μm that had been subjected to a mold release treatment so as to have a thickness of 20 μm, thereby preparing a resin film. A PET film having a thickness of 50 μm was laminated as a cover film.

From the cover film surface, UV light having a main emission wavelength of 400 nm and an illuminance of 1 mW / cm ² was irradiated for 120 seconds. Next, the cover film was peeled off, and the resin film was attached to an acrylic plate or a polycarbonate plate serving as a substrate. Next, the PET film on the reverse side was peeled off, and another acrylic plate or polycarbonate plate was attached to the resin film in the same manner.

  The bonding area was 2.5 cm × 2.5 cm, and a 2 kg rubber roller was reciprocated once on the back side of one acrylic plate during bonding.

After bonding, UV light having a main emission wavelength of 365 nm and an illuminance of 24 mW / cm ² was irradiated for 250 seconds. Next, a peel test was performed according to JIS K 6854-1: 1999, and the strength at the time of peeling was defined as the adhesive strength.

  In the resin sheet obtained by applying the first and second triggers to the micropattern forming material and curing, the Young's modulus in the thickness direction is preferably 1 to 5 MPa. When the Young's modulus is within this range, a very small three-dimensional structure such as a hollow structure, a bridge structure, or a cantilever structure is deposited when laminated on the adherend surface using the transfer method. Even if they exist in the body, they can be bonded without filling them. If the Young's modulus is outside this range, it may be difficult to bond these structures without filling them by the transfer method. In the present specification, the Young's modulus of the micropattern is a value measured by the following method.

Measurement of Young's modulus:
The Young's modulus was measured based on the bulge method that has been conventionally known as the Young's modulus measurement method. That is, a negative pressure is applied to a film to be measured, and the amount of distortion of the film with respect to the negative pressure is measured with a heterodyne displacement meter. A method for calculating the Young's modulus was adopted. Negative pressure was realized using a vacuum system. When the area where the negative pressure is applied to the thin film is circular, the amount of deflection at the portion (the center of the thin film) showing the maximum deflection of the thin film is Δp = (Ath / r ² ) + (BtEh ⁵ / r ⁴ )
There is a relationship. Here, p is a pressure difference from the atmospheric pressure, h is a deflection amount, E is a Young's modulus, r is a radius of a circular region where a negative pressure is applied, t is a thin film thickness, and A and B are constants. Based on this calculation formula, constants A and B were obtained from a standard sample of silicon nitride having a known Young's modulus, and the Young's modulus E of the target film was calculated. The measurement sample was prepared by attaching a film to be measured to a stainless steel plate having a thickness of 2 mm and having a 2 mm round opening formed by anisotropic etching of silicon.

(Micro pattern composite)
The micropattern composite material according to the present invention has a structure in which a micropattern member is laminated on a support. The micro pattern member in this state is a film having a micro penetrating structure or a micro slit structure having an order of a minimum width of 10 μm or less, or a micro periodic structure. The micropattern member does not have an adhesive force as it is, but develops an adhesive property by applying the second trigger. The peeling force of the micropattern member with respect to the support is preferably 0.02 N / 10 mm or less. Thereby, the support can be easily peeled off after the transfer. If the peeling force exceeds this value, it may be difficult to peel off the support after transfer. The peeling force is a value measured by the following method.

(Measurement method of peeling force)
180 degree peeling adhesion test compliant with JIS Z0237: 2000 Test Piece A micropattern composite material in which a micropattern member was laminated on a support made of PET having a thickness of 25 μm was cut into a width of 10 mm to obtain a test piece.

2. Adherent A commercially available acrylic plate (cast product) having a thickness of 2.0 mm was cut into a width of about 50 mm and a length of about 125 mm, and washed with ethanol to obtain an adherend.

3. Test The test piece was laminated on the surface of the adherend from the micropattern member side. The rubber roller was reciprocated once at a speed of 300 mm / min so that a load of 0.2 MPa was applied to the surface of the support of the test piece opposite to the side on which the micropattern member was laminated, that is, the back surface. Thereafter, the laminate in which the test piece was pressure-bonded to the adherend was allowed to stand at 23 ° C. and 50% humidity for 20 minutes.

  After standing, a PET film having a thickness of 25 μm as a support was peeled from the micropattern member in the 180 ° direction at a speed of 300 mm / min, and the peel strength was measured.

(resolution)
The order of resolution of 10 μm or less means that the minimum width dimension such as the width or diameter of a slit or a through hole for forming a flow path or a reaction tank is 10 μm or less, that is, the final dimension part for forming the reaction tank is 10 μm or less It means to be.

(Manufacturing method of micro pattern composite material)
The micropattern member is formed before or after the micropattern forming material is applied or laminated on the support, or after the application or lamination, in addition to the portion that becomes the flow passage or the through hole. A first trigger is applied using a mask having a hole portion as a light shielding portion. As a result, light is not irradiated in the light-shielding portion that becomes the flow path or the through-hole, and light is irradiated in the remaining portion, so that photocrosslinking proceeds. Thereafter, development is performed with an alkaline developer. The uncured curable composition in the portion that has not been irradiated with light is dissolved and removed in the alkaline developer, and a flow path and a through hole are formed. In this manner, a micropattern composite material in which the micropattern member is supported on the support is obtained. The micropattern member includes an unreacted ion polymerizable resin (D) and a photoion polymerization catalyst (E). For this reason, the micropattern member starts an ionic polymerization reaction by light irradiation approximately ten times as much as the light irradiation at the time of micropattern formation, and exhibits a light delayed adhesion function.

  As the support, it is possible to use a support made of an appropriate material that can withstand the alkaline developer when the micropattern member is formed. However, in order to facilitate the peeling of the support after the transfer, the support is preferably made of a synthetic resin film having flexibility. Examples of such a synthetic resin film include an appropriate synthetic resin film such as a polypropylene film and a polyethylene terephthalate (PET) film. The thickness of the support is also not particularly limited because it is peeled off after transfer, but it may be about 10 μm to 100 μm for easy handling.

  The surface of the support on which the micropattern member is laminated is preferably subjected to a release treatment. Thereby, the final support can be easily peeled off. The mold release treatment can be performed by appropriately applying a general silicon release material or a fluorine release material.

  A releasable protective film may be laminated on the surface of the micropattern member to be adhered to the adherend. In that case, it is preferable to adjust the release property of the support so as to be slightly lower than the release property of the protective film.

(Manufacturing method of micro three-dimensional structure substrate)
In the present invention, in order to obtain a micro three-dimensional structure substrate, first, the micro pattern composite material is prepared. Next, the micropattern member of the micropattern composite material is laminated on a separately prepared substrate. Before or after the lamination of the micropattern member, a second trigger, for example, light is applied to the micropattern member to cause the micropattern member to exhibit adhesiveness. Thereafter, the micropattern member of the micropattern composite material is pressed against the surface of the substrate while applying pressure using a pressurizing jig or device such as a hand rubber roller or a laminator. At the time of pressure bonding, the pressure pressure and the number of times of the pressure jig and the device are adjusted as necessary.

  The ion polymerization of the above-mentioned ion polymerizable resin (D) proceeds even after the light irradiation is stopped.

  That is, the adhesion of the micropattern member to the adherend is performed by ion polymerization of the ion polymerizable resin (D) in the micropattern forming material described above. In this case, when the ion polymerizable resin (D) is polymerized by photocationic polymerization, the polymerization reaction proceeds even after the photocationic polymerization is stopped. Therefore, the irradiation of light may be stopped before the lamination and pressure bonding of the micropattern member.

  In addition, you may provide a 2nd trigger after lamination | stacking and crimping | bonding, without providing 2nd triggers, such as light, before lamination | stacking.

  In addition, when light is irradiated before laminating | stacking a micropattern member on a board | substrate, you may accelerate | stimulate hardening by heating after lamination | stacking.

  Moreover, the said heating is performed in order to accelerate hardening of an ion polymerizable resin (D) by the effect | action of a thermosetting agent, when a thermosetting agent is used together.

  In the manufacturing method according to the present invention, preferably, after the micropattern member supported by the support is pressure-bonded to the substrate, the support is peeled from the micropattern member. Thus, the micropattern member can be pressure-bonded to the substrate by a transfer method. In this case, the micropattern member on the micro three-dimensional structure substrate from which the support has been peeled is used as the next adherend, and a new micropattern composite material is laminated thereon, and the micropattern member is formed as described above. You may crimp to. Thereafter, the support of the micropattern composite material newly bonded onto the micropattern on the micro three-dimensional structure substrate as the adherend is peeled off. By doing so, it is also easy to obtain a micro three-dimensional structure laminate in which a multiplicity of micropattern members are laminated by sequentially transferring and joining a large number of micropattern members while precisely aligning them.

  Furthermore, another member such as a film different from the micropattern may be laminated on one or more micropattern members laminated on the substrate, and bonded and pressure-bonded. In this case, the other member peels the support from one or more micropattern members laminated on the substrate, and the one or more micropattern members laminated on the substrate completes the adhesion reaction. Before being laminated, they are laminated, bonded and crimped. As such another film member, an appropriate film material that is adhesive or non-adhesive can be used. Examples of the material constituting such a film material include punched products such as metals, resins, and cellulose, synthetic resin thin molded products, thin foams, woven fabrics, nonwoven fabrics, and laminates prepared in advance. Can be mentioned.

  The other film material may be formed with a micro pattern or may not be formed. It does not specifically limit about the thickness of another film material, For example, it can be referred to as about 10 micrometers-2 mm.

  In addition, after the said micro pattern member and another member are crimped | bonded, the 2nd trigger may be given to the said micro pattern member further.

  By using the micro pattern member for a micro three-dimensional structure of the present invention, a micro fluid element such as a micro well, a micro chamber, a micro channel, a micro valve, a micro mixer, and a micro pump can be produced. Moreover, the partition, the spacer, and the dielectric layer of the electrode array constituting the optical waveguide, the cell culture substrate, and the flat panel display electronic paper can be formed by the micropattern member of the present invention. Furthermore, a color filter, a fluorescent cell, and a black matrix can be produced by adding a dye or a fluorescent substance. In addition, metal particles can be dispersed in the material for forming a micropattern of the present invention and used for forming wirings, microcoils, or bumps. In addition, the micropattern forming material of the present invention is combined with a plating process or an ink jet technique to provide a chemical electrode array, pressure sensor array, resistor array, bio battery cell, dye solar cell, photonic crystal, movable mirror array, resistor. An array, a capacitor array, a heater array, a bimetal array, a micro relay array, a nozzle array, an emulsified chip, and a fine lost core material can be formed.

  According to the material for forming a micropattern according to the present invention, a micropattern member can be obtained by first patterning by partially applying the first trigger. Since the obtained micropattern member does not exhibit adhesiveness as it is, positioning can be easily performed when the micropattern member is laminated on another member such as a substrate. In addition, by applying the second trigger before or after the micropattern member is laminated on the substrate or the like, the micropattern member exhibits adhesiveness, and the micropattern member is reliably attached to the substrate or another micropattern member. Glued. Therefore, it is possible to easily obtain the micro three-dimensional structure substrate of the present invention by stacking the micro pattern members having the micro flow paths and the like with high accuracy.

  In addition, by changing the types and strengths of the first and second triggers, micropattern members having various micropatterns can be formed with high accuracy.

  In the method for producing a micropattern composite material according to the present invention, the micropattern composite material according to the present invention is laminated on a support, or after the lamination, the first trigger is applied and patterning is performed. The material can be easily obtained.

  According to the method for manufacturing a micro three-dimensional structure substrate according to the present invention, the micropattern of the present invention is performed by performing the patterning step including applying the first trigger using the micropattern forming material according to the present invention. After obtaining the composite material, the micropattern member of the micropattern composite material is pressure-bonded to the substrate surface, and a fine channel suitable for a microchip or the like is formed simply by applying a second trigger before or after pressure bonding. In addition, it is possible to easily obtain a small three-dimensional structure substrate.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention.

Example 1
(A) As an alkali-soluble binder resin, Cyclomer P ACAZ300 (manufactured by Daicel Cytec) (40 parts by weight),
(B) As an oligomer (b2) having a radical polymerizable double bond, EBECRYL 4858 (manufactured by Daicel Cytec) (30 parts by weight) and a compound (b3) having two or more radical polymerizable double bonds in one molecule , Light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) (10 parts by weight),
(C) Irgacure 819 (manufactured by Ciba Specialty Chemicals) (1 part by weight) as a photo radical generator,
(D) As an ion polymerizable resin, Epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.) (20 parts by weight),
(E) As a photoion polymerization catalyst, Optomer SP-170 (manufactured by ADEKA) (2 parts by weight),
Furthermore, 40 parts by weight of ethyl acetate was added as a solvent, and the mixture was stirred and mixed under light shielding to obtain a micropattern forming material comprising a uniform resin composition solution for casting.

  The micropattern-forming material obtained as described above was applied onto a polycarbonate film as a support using an applicator so that the thickness after drying was 100 μm, and dried at 110 ° C. for 5 minutes. Next, a photomask 1 shown in FIG. In the photomask 1, a light-shielding thin film 3 is bonded to a transparent glass plate 2 at a portion where a flow path as a micro pattern is formed. The planar shape of the light-shielding thin film 3 is a shape corresponding to the micropattern to be formed. The light-shielding thin film 3 is made of a metal chromium thin film that shields light.

Next, as shown in FIG.3 (b), the said photomask 1 is arrange | positioned on the composite sheet with which the resin composition layer 5 was coated on the polycarbonate film 4 as a support body, and a metal halide lamp ( The product was irradiated with ultraviolet light having a wavelength of 400 nm so that the energy amount was 100 mJ / cm ² . By irradiation, the ultraviolet light was irradiated onto the resin composition layer 5 in a portion where the light-shielding thin film 3 was not present, and the resin composition layer 5 was not exposed below the light-shielding thin film 3. Thereafter, after light irradiation, development was performed using a 0.24% tetramethylammonium hydroxide aqueous solution (TMAH) as a developer. That is, the composite sheet was dipped in 0.24% TMAH and pulled up to remove the unreacted resin composition layer 5 that was not irradiated with light.

  As a result, as shown in FIG. 1, a micropattern composite material 6 in which a film-like micropattern member 5A was formed on a polycarbonate film 4 was obtained. In the micropattern member 5A, a flow path having a shape corresponding to a portion of the photomask 1 where the light-shielding thin film 3 is provided is formed. However, the lower polycarbonate film 4 exists at the bottom of the flow path. Therefore, a bottomed fine channel is formed. The resin composition 5 of the uncured portion was completely removed from the flow path portion of the micropattern composite material 6 thus obtained.

In the micropattern composite material 6 shown in FIG. 1, the surface of the micropattern composite material 6 has slight adhesiveness, but does not have a strong adhesive force as it is. The adhesion of the micropattern member of the present composition to the polycarbonate substrate obtained after the application of the first trigger measured by the above-described test method “Measurement of adhesion” was 0.04 N / cm ² .

Next, the micropattern member was irradiated with ultraviolet light having a wavelength of 365 nm so as to have an energy amount of 4000 mJ / cm ² . After the irradiation, the adhesion strength to the polycarbonate substrate was determined in the same manner, and the adhesion strength was increased to 1.1 N / cm ² .

(Example 2)
A micropattern composite material was obtained in the same manner as in Example 1 except that the following composition was used as the micropattern forming material. The resin composition of the uncured portion was completely removed from the flow path portion of the obtained micropattern composite material. The surface of the micropattern composite material 6 has slight adhesiveness but does not have a strong adhesive force as it is. The adhesion of the micropattern member of this composition to the polycarbonate substrate obtained after applying the first trigger measured by the test method “Measurement of Adhesion” described above was 0.03 N / cm ² .

Next, the micropattern member was irradiated with ultraviolet light having a wavelength of 365 nm so as to have an energy amount of 4000 mJ / cm ² . After the irradiation, the adhesion strength to the polycarbonate substrate was determined in the same manner, and the adhesion strength was increased to 0.9 N / cm ² .

(A) As an alkali-soluble binder resin, ARUFON UC-3000 (manufactured by Toa Gosei Co., Ltd.) (40 parts by weight),
(B) As an oligomer (b2) having a radical polymerizable double bond, EBECRYL 4858 (manufactured by Daicel Cytec) (30 parts by weight) and a compound (b3) having two or more radical polymerizable double bonds in one molecule , Light acrylate TMP-A (manufactured by Kyoeisha Chemical Co., Ltd.) (10 parts by weight),
(C) Irgacure 819 (manufactured by Ciba Specialty Chemicals) (1 part by weight) as a photo radical generator,
(D) As an ion polymerizable resin, Epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.) (20 parts by weight),
(E) As a photoion polymerization catalyst, Optomer SP-170 (manufactured by ADEKA) (2 parts by weight),
Ethyl acetate (40 parts by weight).

(Example 3)
A micropattern composite material was obtained in the same manner as in Example 1 except that the following composition was used as the micropattern forming material. The resin composition of the uncured portion was completely removed from the flow path portion of the obtained micropattern composite material. The surface of the micropattern composite material 6 has slight adhesiveness but does not have a strong adhesive force as it is. The adhesion force of the micropattern member of the present composition to the polycarbonate substrate obtained by applying the first trigger measured by the above-described test method “Measurement of adhesion strength” was 0.025 N / cm ² .

Next, the micropattern member was irradiated with ultraviolet light having a wavelength of 365 nm so as to have an energy amount of 4000 mJ / cm ² . After the irradiation, the adhesion strength to the polycarbonate substrate was determined in the same manner, and the adhesion strength was increased to 0.75 N / cm ² .

(A) As an alkali-soluble binder resin, polybutyl acrylate resin (40 parts by weight) copolymerized with 20% by weight of acrylic acid,
(B) As an oligomer (b2) having a radical polymerizable double bond, EBECRYL 4858 (manufactured by Daicel Cytec) (30 parts by weight) and a compound (b3) having two or more radical polymerizable double bonds in one molecule UA324 (manufactured by Shin-Nakamura Chemical Co., Ltd.) (10 parts by weight)
(C) Irgacure 819 (manufactured by Ciba Specialty Chemicals) (1 part by weight) as a photo radical generator,
(D) As an ion polymerizable resin, Epicoat 834 (manufactured by Japan Epoxy Resin Co., Ltd.) (20 parts by weight),
(E) As a photoion polymerization catalyst, Optomer SP-170 (manufactured by ADEKA) (2 parts by weight),
Ethyl acetate (40 parts by weight).

  However, the polybutyl acrylate resin comprises 20 parts by weight of methyl methacrylate, 50 parts by weight of butyl acrylate, 30 parts by weight of acrylic acid, 50 parts by weight of ethyl acetate as a polymerization solvent, a stirrer and a cooling reflux tube. The mixture was heated in a water bath while being stirred and polymerized at the boiling point of ethyl acetate.

  As the polymerization initiator, Perhexa TMH (manufactured by NOF Corporation) and Parroyl 355 (manufactured by NOF Corporation) were used. When the total amount of methyl methacrylate, butyl acrylate and acrylic acid is 100 parts by weight, Perhexa TMH is added at 0.035 parts by weight at the start of the polymerization reaction, 0.035 parts by weight after 0.5 h, 0.1 parts by weight after 1.0 h, and 0.05 parts by weight after 1.5 h after the start of the polymerization reaction, where Parroyl 355 is also taken as 100 parts by weight of the total of methyl methacrylate, butyl acrylate and acrylic acid. Then, 0.05 parts by weight after 2.5 hours, 0.75 parts by weight after 4.0 hours, and 1.5 parts by weight after 7.0 hours. The polymerization reaction was performed for 10 hours.

Example 4
(A) As the alkali-soluble binder resin (A), the microbutyl acrylate resin composition was changed to 80 parts by weight of butyl acrylate and 20 parts by weight of methyl methacrylate. A pattern composite was obtained. In the flow path part of the obtained micropattern composite material, the resin composition of the uncured part remained slightly. The adhesion of the micropattern member of the present composition to the polycarbonate substrate obtained by applying the first trigger measured by the above-described test method “Measurement of adhesion” was 0.02 N / cm ² .

Next, the micropattern member was irradiated with ultraviolet light having a wavelength of 365 nm so as to have an energy amount of 4000 mJ / cm ² . After the irradiation, the adhesion strength to the polycarbonate substrate was determined in the same manner, and the adhesion strength was increased to 0.73 N / cm ² .

(Example 5)
On the micropattern member 5A of the micropattern composite material 6 obtained in Example 1, an acrylic resin plate 7 having a thickness of 1 mm having through holes 7a to 7c is laminated after precision positioning by a contact alignment method. A laminate was obtained. The laminate was lightly squeezed with a rubber roller and then sandwiched between two 2 mm thick quartz glass plates to obtain a sandwiched sample. While applying a back pressure of 0.1 MPa to the sandwiched sample thus obtained, ultraviolet light having a wavelength of 365 nm or less from the outside of the quartz glass plate on the side where the polycarbonate film 4 is arranged is 4000 mJ / cm ^2. Irradiation was carried out so that the amount of energy was. In this way, the acrylic resin plate 7 and the micropattern composite material 6 were joined. Thereby, as shown in FIG. 2, the microchip 8 which consists of a micro three-dimensional structure board | substrate with which the acrylic resin plate 7 was joined to the micro pattern composite material 6 was obtained. In addition, the standing time until sufficient adhesive force was expressed was as short as 6 hours. Therefore, sufficient adhesive force was developed in a relatively short time.

  As described above, it was confirmed that the slightly sticky film-like micropattern member 5A that does not have adhesiveness as it is and the acrylic resin plate 7 are firmly bonded by the irradiation of the ultraviolet light. It should be noted that the capillary was adhered to any of the through holes 7a to 7c of the acrylic resin plate 7, and the ink was injected using a syringe and left to stand overnight with a pressure of 0.2 MPa. No leakage was observed.

(Example 6)
The film-like micropattern member 5A of the micropattern composite material 6 obtained in Example 1 was irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 4000 mJ / cm ² . Thereafter, the acrylic resin plate 7 having a thickness of 1 mm having the through holes 7a to 7c used in Example 4 was precisely positioned and laminated on the micropattern member 5A side by a contact alignment method to obtain a laminate. After lightly squeezing this laminated body with a rubber roller, an iron plate having a thickness of 2 mm was placed on the surface of the laminated body and allowed to stand for 6 hours. Thereby, the microchip 8 having the same structure as shown in FIG. 2 was obtained, in which the acrylic resin plate 7, the micropattern member 5A, and the polycarbonate film 4 were joined. Thus, even when the micropattern member 5A and the acrylic resin plate 7 were brought into close contact with each other after the light irradiation, it was confirmed that the adhesion proceeded due to the delayed curing reaction and was sufficiently adhered. In addition, the standing time until sufficient adhesive force was expressed was as short as 6 hours. Therefore, sufficient adhesive force was developed in a relatively short time.

  Also in Example 6, the capillary was adhered to any of the through holes 7a to 7c of the acrylic resin plate 7, the ink was injected using a syringe, and the pressure of 0.2 MPa was applied and left overnight. No peeling or liquid leakage was observed on the adhesive surface.

(Example 7)
Except that the film-like micropattern member 5A of the micropattern composite material 6 obtained in Example 1 was irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 80 mJ / cm ^2. 6 was obtained in the same manner.

  As described above, even when the micropattern member 5A and the acrylic resin plate 7 were brought into close contact with each other after the light irradiation, the adhesion progressed due to the delayed curing reaction. I had to put it.

  Also in Example 7, the capillary was adhered to any one of the through holes 7a to 7c of the acrylic resin plate 7, the ink was injected using a syringe, and the pressure of 0.2 MPa was applied and left overnight. No peeling or liquid leakage was observed on the adhesive surface.

(Example 8)
Except that the film-like micropattern member 5A of the micropattern composite material 6 obtained in Example 1 was irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 200 mJ / cm ^2. 6 was obtained in the same manner.

  As described above, even when the micropattern member 5A and the acrylic resin plate 7 were brought into close contact with each other after the light irradiation, the adhesion progressed due to the delayed curing reaction, but for 9 hours until the sufficient adhesiveness was developed. I had to put it.

  Also in Example 8, the capillary was adhered to any of the through holes 7a to 7c of the acrylic resin plate 7, the ink was injected using a syringe, and the pressure was 0.2 MPa, which was left overnight. No peeling or liquid leakage was observed on the adhesive surface.

Example 9
Except that the film-shaped micropattern member 5A of the micropattern composite material 6 obtained in Example 1 was irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 8000 mJ / cm ^2. 6 was obtained in the same manner.

  In the case of Example 9, since the energy amount of the second trigger irradiation is large, the curing reaction proceeds too much before the micropattern member 5A and the acrylic resin plate 7 are brought into close contact with each other, and the unevenness of the unadhered portion is adhered to the bonded portion. Was slightly recognized.

  Also in Example 9, the capillary was adhered to any of the through holes 7a to 7c of the acrylic resin plate 7, the ink was injected using a syringe, and the pressure of 0.2 MPa was applied and left overnight. No peeling or liquid leakage was observed on the adhesive surface.

(Example 10)
Except that the film-shaped micropattern member 5A of the micropattern composite material 6 obtained in Example 1 was irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 10200 mJ / cm ^2. 6 was obtained in the same manner.

  In the case of Example 10, since the energy amount of the second trigger irradiation is larger, the curing reaction proceeds too much before the micropattern member 5A and the acrylic resin plate 7 are brought into close contact with each other. Some unevenness was observed.

  Also in Example 10, when a capillary is adhered to any of the through holes 7a to 7c of the acrylic resin plate 7, the ink is injected using a syringe, and the pressure of 0.2 MPa is applied and left overnight. No peeling or liquid leakage was observed on the adhesive surface.

(Example 11)
A film is formed on the polyethylene terephthalate film in the same manner as in Example 1 except that a commercially available polyethylene terephthalate film subjected to surface release treatment is used as a support and the photomask 11 shown in FIG. 4 is used. A micropattern composite material having a micropattern member formed thereon was prepared. In the photomask 11 shown in FIG. 4, a large number of disc-shaped light-shielding thin films 12 and a rectangular frame-shaped light-shielding thin film 13 along the outer peripheral edge are printed on a light-transmitting resin sheet 14.

  FIG. 5 shows a micropattern composite material in which a micropattern member 17 obtained by using the photomask 11 is laminated on the release-treated polyethylene terephthalate film as a support.

The micropattern member 17 on the support is not a sticking force as it is, but is a slightly sticky film that develops adhesiveness when irradiated with light, and a through hole is formed in a portion corresponding to the light shielding thin film 12. Is formed. Thereafter, the micropattern member 17 side of the micropattern composite material was laminated on a circuit board 16 made of an acrylic plate having a thickness of 1 mm in which a plurality of printed electrodes 18 were formed in a matrix, thereby obtaining a laminate. . After this laminate was lightly crushed by applying a force in the thickness direction of the laminate using a rubber roller, ultraviolet light having a wavelength of 365 nm or less from the side of the polyethylene terephthalate film, which is a support for the micropattern composite material, was 4000 mJ / It irradiated so that it might become the energy amount of cm < ² >, and the said circuit board 16 made from an acrylic board, and the said micro pattern member 17 were adhere | attached. Thereafter, the polyethylene terephthalate film as a support is peeled off, and a chemical electrode array plate with microwells in which printed electrodes 18 as shown in FIG. 15 was produced. Thus, by forming a micro three-dimensional structure substrate by transfer adhesion, the chemical electrode array plate 15 with microwells could be formed without contaminating the peripheral edge of the printed electrode 18.

Example 12
A micropattern composite material was obtained in the same manner as in Example 1 except that a polyethylene terephthalate film whose surface was subjected to a release treatment was used as a support and the photomask 21 shown in FIG. 6 was used. In the photomask 21, a plurality of square light-shielding portions 21a are arranged in a matrix. Next, the micropattern member of the obtained micropattern composite material was laminated | stacked on the polycarbonate plate of thickness 0.5mm which has a through-hole, and the laminated body was obtained. After lightly squeezing this laminate with a rubber roller so as to apply pressure in the thickness direction, the polyethylene terephthalate film, which is the support, is peeled off, and another 0.5 mm thick polycarbonate having another through hole on it. The plates were laminated to obtain a laminate in which the micropattern member was sandwiched between two polycarbonate plates. This laminate is irradiated with ultraviolet light having a wavelength of 365 nm or less so as to have an energy amount of 4000 mJ / cm ² , the micropattern member and the polycarbonate plates on both sides are bonded, and openings are formed on the upper and lower surfaces shown in FIG. A microplate 23 having a micro three-dimensional structure having Thus, it was possible to easily produce a micro three-dimensional structure sandwiched between two polycarbonate plates different from the support supporting the micropattern member.

  A sample for Young's modulus measurement was obtained in the same manner as described above except that a 2 mm thick stainless steel plate having a 2 mm diameter opening was used instead of the polycarbonate plate, and that front exposure was performed without using a photomask. It was. The Young's modulus of the micropattern as the obtained sample was 3.5 MPa.

(Example 13)
Except for using a polyethylene terephthalate film subjected to a release treatment as a support, and using each of the photomasks 31 and 32 shown in FIGS. 8A and 8B, in the same manner as in Example 1, Four micropattern composites having a micropattern member formed on a support were produced. In the photomasks 31 and 32, a plurality of striped light shielding portions 31a and 32a extending in parallel with each other are provided. The obtained one micropattern composite material is taken up as an adherend, and on one micropattern member of the adherend, another micropattern composite micropattern member has a plurality of parallel extending patterns. Lamination was performed so as to intersect the pattern direction on the adherend side, and the laminate was lightly squeezed with a rubber roller. Ultraviolet light having a wavelength of 365 nm or less was irradiated from the support side so that the energy amount was 4000 mJ / cm ² , the adherend and the micropattern member were bonded, and then the support was peeled from the micropattern member. Thereafter, another micropattern composite material was stacked in the same manner, and photoadhesion and peeling of the support were performed. This operation was repeated to obtain a photonic crystal laminate 41 in which four micropatterns were laminated so that the extending directions of the adjacent micropatterns in the thickness direction were orthogonal to each other as shown in a perspective view in FIG. FIG. 10 is an electron micrograph of the obtained photonic crystal laminate 41, and FIG. 11 is an electron micrograph showing a portion of the bonding surface cut by a microtome.

(Example 14)
A microfluidic chip was manufactured by laminating five layers by the same method as in Example 13. An optical micrograph of the produced microfluidic chip is shown in FIG. The second and fourth layers have flow paths by slits and are connected by a third layer through-hole. The first and fifth layers serve as a lid. It was possible to finish bonding all five layers in about 10 minutes. The minimum width seen in the second and fourth layers is 10 μm, which constitutes a passive valve using Laplace pressure.

(Example 15)
A microchip was obtained in the same manner as in Example 5 except that each of the micropattern composite materials of Example 2 and Example 3 was used. A micro-adhesive film-like micropattern member A and an acrylic chip were obtained. It was confirmed that the resin plate 7 was firmly adhered to the resin plate 7 by irradiation with ultraviolet light.

1 is a perspective view of a micropattern composite material produced in Example 1. FIG. It is a perspective view which shows the microchip by which the acrylic resin plate as another member was laminated | stacked on the micro pattern composite material produced in Example 1. FIG. (A) is a figure which shows the photomask used in Example 1, (b) is typical front sectional drawing which shows the exposure process for the photolithography using a photomask. 10 is a perspective view showing a photomask used in Example 11. FIG. FIG. 12 is a perspective view showing a chemical electrode array plate with microwells produced in Example 11. 14 is a plan view showing a photomask used in Example 12. FIG. 14 is a perspective view showing a minute three-dimensional structure formed in Example 12. FIG. (A) And (b) is a top view which shows each photomask used in Example 13. FIG. 14 is a perspective view showing a photonic crystal structure obtained in Example 13. FIG. It is a figure which shows the electron micrograph of the photonic crystal structure obtained in Example 13. FIG. It is a figure which shows the electron micrograph of the cross-sectional part which cut | disconnected the adhesion surface in the photonic crystal structure obtained in Example 13 with the microtome. It is a figure which shows the optical microscope photograph of the microfluidic chip | tip obtained in Example 14. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photomask 2 ... Glass plate 3 ... Light-shielding thin film 4 ... Polycarbonate film 5 ... Resin composition layer 5A ... Micro pattern member 6 ... Micro pattern composite material 7 ... Acrylic resin plate 7a, 7b, 7c ... Through-hole 8 ... Microchip 11 ... Photomask 12 ... Light-shielding thin film 13 ... Light-shielding thin film 14 ... Resin sheet 15 ... Chemical electrode array plate with microwells 16 ... Circuit board 17 ... Micropattern member 17a ... Microwell 18 ... Printed electrode 21 ... Photomask 21a ... Light-shielding part 23 ... Microplate 31 ... Photomask 31a ... Light-shielding part 32 ... Photomask 32a ... Light-shielding part 41 ... Photonic crystal laminate

Claims (16)

A material for forming a micropattern for forming a micropattern member,
By providing a second trigger different from the first trigger after the first trigger is partially applied and partially cured, and after a portion other than the partially cured portion is removed A material for forming a micropattern that is cured and exhibits adhesiveness.   The material for forming a micropattern according to claim 1, wherein the first trigger is light, and the second trigger is light. An alkali-soluble binder resin (A);
A radically polymerizable compound (B);
A photo radical generator (C);
An ion polymerizable resin (D);
The material for forming a micropattern according to claim 2, comprising a photoion polymerization catalyst (E).   The material for forming a micropattern according to claim 3, wherein the photoradical generator (C) is a photoradical generator that generates radicals when light having a wavelength of 400 nm or more is applied.   The ratio of the applied total amount (P2) of the second trigger to the applied total amount (P1) of the first trigger is P2 / P1 in the range of 1 to 100, according to any one of claims 2 to 4. The material for micropattern formation as described.   The material for forming a micropattern according to claim 1, wherein the first trigger is light and the second trigger is heat. An alkali-soluble binder resin (A);
A radically polymerizable compound (B);
A photo radical generator (C);
An ion polymerizable resin (D);
The material for forming a micropattern according to claim 6, comprising a thermosetting agent (F). A support, and a micropattern member formed on the support and forming a micropattern,
The micropattern member is made of a material obtained by applying a first trigger to the micropattern forming material according to any one of claims 1 to 7, and after the second trigger is applied A micro-pattern composite material that exhibits adhesiveness.   The micropattern composite material according to claim 8, wherein a Young's modulus in a thickness direction of the micropattern member in the micropattern composite material is 1 to 5 MPa.   The micropattern composite material according to claim 8 or 9, wherein a peeling force of the micropattern member before the second trigger is applied to the support is 0.02 N / 10 mm or less. A step of laminating the micropattern forming material according to any one of claims 1 to 7 on a support;
Before or after laminating the micropattern forming material on the support, a micro trigger is formed by applying a first trigger and patterning the micropattern forming material, thereby supporting the micropattern forming material. And a step of obtaining a micropattern composite material having a body and a micropattern member. A step of laminating the micropattern forming material according to any one of claims 1 to 7 on a support;
After the micropattern forming material is laminated on the support, a micropattern member is formed by patterning the micropattern forming material by applying a first trigger, thereby forming the support and the micropattern member. Obtaining a micropattern composite having
Applying a second trigger to the micropattern member to develop adhesiveness in the micropattern member;
And a step of pressure-bonding the micropattern member of the micropattern composite material to the surface of the substrate.   The method for manufacturing a micro three-dimensional structure substrate according to claim 12, further comprising a step of peeling the support from the micro pattern member after the micro pattern member is pressure-bonded to the substrate.   After the support is peeled off, a step of further pressing the micropattern member of the new micropattern composite material on the micropattern member and a step of peeling the support of the new micropattern composite material are provided. The manufacturing method of the micro three-dimensional structure board | substrate of Claim 13.   15. The method according to claim 13, further comprising a step of laminating and adhering another member to the micropattern member before the support is peeled off and the exposed micropattern member completes an adhesion reaction. A method for manufacturing a micro three-dimensional structure substrate.   The method for manufacturing a micro three-dimensional structure substrate according to any one of claims 12 to 15, wherein the second trigger is applied to the micro pattern member after the micro pattern member is pressure-bonded.