JP2023171719A - Photosensitive resin laminate for micro flow channel devices - Google Patents

Abstract

To provide a photosensitive resin laminae for micro flow channel devices, which can be used to produce a micro flow channel device with superior capability to detect a target substance through fluorescence emission.SOLUTION: A photosensitive resin laminate for micro flow channel devices is provided, comprising a support film and a photosensitive resin composition layer. The photosensitive resin laminate for micro flow channel devices exhibits a transmittance of 80% or greater for either or both of 515 nm and 600 nm wavelength after being exposed, and an adhesion strength between the support film and the photosensitive resin composition layer of 3 to 100 gf/inch, inclusive.SELECTED DRAWING: None

Description

The present invention relates to a photosensitive resin laminate for microchannel devices.

Microfluidic devices (also referred to as microfluidic devices, microfluidic chips, μTAS (Micro Total Analysis Systems), LOC (Lab on a Chip), microreactors, etc.) are microelectromechanical devices based on microfluidics. It is known as a device that includes a microcircuit formed using microfabrication technology such as (MEMS) technology, and is being used for various purposes such as biotechnology research, drug discovery, diagnosis, testing, and chemical engineering. In particular, in recent years, there has been increasing interest in the use of microchannel devices in home health care, telemedicine, on-the-spot clinical testing (POCT), and the like.

Conventionally, the manufacturing methods for microchannel devices have been injection molding, mold molding, and glass etching, but instead of these, a resin pattern for the channel is formed on the base material by photolithography, and then a lid material (sealer) is formed. A method of joining (materials) has been proposed (Patent Documents 1 to 3).

Patent Document 1 describes (A) a bisphenol A-novolac epoxy resin with a specific structure, (B) an epoxy resin with a specific structure, and (C) one or more cationic photoinitiators (photoacid generators or PAGs). Permanent photoresist compositions are described that can be formed by ultraviolet lithography and are also useful in the production of microfluidic components, etc., including (D) one or more solvents. .

Patent Document 2 describes a method for manufacturing a microfluidic chip package or assembly, which includes forming a block including a microfluidic structure on a substrate, pasting a cover film to cover the block, and the steps of: It is stated that a dry film resist is preferred as the film.
Patent Document 3 describes a step of forming a resin layer from a photosensitive resin composition having a specific structure on a support, a step of exposing and developing a part of the resin layer, and a step of forming a lid material on the developed resin layer. According to the method for manufacturing a microfluidic device, which includes a step of placing a laminate to obtain a laminate, and a step of exposing the obtained laminate to ultraviolet light, the patterned resin layer after litho has sufficient strength and tack. It is described that by having this, a microfluidic device having a good flow path etc. can be manufactured.

Special Publication No. 2007-522531 Special table 2016-529116 publication JP2017-119340A

Microchannel devices are used for analysis of trace substances, chemical reactions, etc. in various applications as described above, and fluids (liquids or gases) according to each application are introduced into the microchannels. Components that come into contact with fluids in microchannels (e.g., partition materials and sealing materials) have poor resistance to fluids (e.g., water resistance for aqueous fluids), causing the components to swell with the fluid, or have defects such as cracks in the components. In this case, the intended flow of the fluid within the microchannel is not ensured, and in some cases, the fluid leaks out of the microchannel, which impairs the accuracy of analysis, chemical reactions, and the like. When using a photosensitive resin laminate (also called dry film resist or dry film photoresist) having a support film and a photosensitive resin composition layer, the properties of the member can be changed by changing the composition of the photosensitive resin composition. (Water resistance, organic solvent resistance, mechanical properties, etc.) can be easily designed, so resistance to fluids and crack resistance can be appropriately controlled depending on the application, and analysis, chemical reactions, etc. can be performed with high precision. can. In addition, since the photosensitive resin laminate can be pattern-exposed, it is possible to form a member with excellent dimensional accuracy without requiring a mold or the like (that is, with less equipment cost).

In analyzes, chemical reactions, and the like using microchannel devices, the presence of a target substance is often detected by emitting a light emission signal from the target substance by irradiating light with a specific wavelength. For such fluorescence detection, for example, a fluorescein compound is often used to detect an excitation wavelength of about 490 nm and an emission wavelength of about 515 nm. Further, a fluorescence microscope with an excitation wavelength of 510 to 560 nm and a detection wavelength of 590 nm or more may be used. Members formed using photosensitive resin laminates have excellent resistance to fluids, crack resistance, and dimensional accuracy, but they emit light when irradiated with light of a specific wavelength, which hinders the desired fluorescence detection of target substances. There was a problem.

Therefore, the problem to be solved by the present invention is to provide a photosensitive resin laminate for a microchannel device that has excellent detectability of a target substance by fluorescence emission.

The present disclosure includes the following aspects.
[1] A photosensitive resin laminate for a microchannel device comprising a support film and a photosensitive resin composition layer,
The photosensitive resin laminate for a microchannel device has a transmittance of 80% or more at one or both wavelengths of 515 nm and 600 nm after exposure,
The adhesion strength between the support film and the photosensitive resin composition layer is 3 gf/inch or more and 100 gf/inch or less,
Photosensitive resin laminate for microchannels.
[2] The photosensitive resin laminate for microchannels according to the above aspect 1, which is for direct exposure.
[3] The photosensitive resin composition layer is composed of a photosensitive resin composition having a ratio (I/O) of inorganic value (I) to organic value (O) of 1.0 or less. , the photosensitive resin laminate for microchannels according to Aspect 1 or 2 above.
[4] The photosensitive resin laminate for microchannels according to any one of Aspects 1 to 3, wherein the photosensitive resin composition layer has an elastic modulus of 2 GPa or less and a breaking elongation of 30% or more after exposure.
[5] The photosensitive resin laminate for a microchannel according to any one of Aspects 1 to 4 above, wherein the photosensitive resin composition layer has a thickness of 100 μm or more.
[6] Any of the above embodiments 1 to 5, in which the thickness of the photosensitive resin composition layer is such that the development time per 25 μm with a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. is 15 to 50 seconds/25 μm. A photosensitive resin laminate for microchannels according to the invention.
[7] The photosensitive resin composition layer includes (a) an alkali-soluble polymer having a carboxyl group, (b) an addition polymerizable monomer, and (c) a photopolymerization initiator,
(b) The addition polymerizable monomer is the following (Formula I):
C-((CH ₂ )R ¹ )((CH ₂ )R ² )((CH ₂ )R ³ )((CH ₂ )R ⁴ )
...(Formula I)
(In the formula, R ¹ to R ⁴ each independently represent a monovalent organic group.)
The microflow according to any one of aspects 1 to 6 above, which is composed of a composition containing 50% by mass or more of (b) an addition polymerizable monomer, a monomer having a structure shown by and having a molecular weight of 200 to 600. Photosensitive resin laminate for road use.

According to the present invention, it is possible to provide a photosensitive resin laminate for a microchannel device, which provides a microchannel device with excellent detectability by fluorescence emission of a target substance.

FIG. 1 is a diagram showing a flow path pattern formed in an example.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, modes for carrying out the present invention (hereinafter abbreviated as "embodiments") will be described in detail. Note that the present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

[Photosensitive resin laminate]
This embodiment provides a photosensitive resin laminate for a microchannel device, which includes a support film and a photosensitive resin composition layer. Note that "composed of a support film and a photosensitive resin composition layer" means that the laminate is substantially composed of a support film and a photosensitive resin composition layer, but it does not impair the effects of the present invention. This means that it does not exclude the possibility that other elements exist. The photosensitive resin laminate for microchannel devices according to the present embodiment (hereinafter also simply referred to as "photosensitive resin laminate") has characteristics particularly suitable for forming microchannels by photolithography, such as , it can be used as a partition material, a lid material, etc. of a microchannel.

In one embodiment, the photosensitive resin laminate has a transmittance of 80% or more at one or both wavelengths of 515 nm and 600 nm after exposure. The transmittance is a value measured by entering light with wavelengths of 515 nm and 600 nm from the exposed photosensitive resin composition layer side. The transmittance is 80% or more, preferably 82% or more, more preferably 84% from the viewpoint of obtaining the desired detectability by fluorescence of the target substance, particularly from the viewpoint of detecting the luminescence of the fluorescein compound. It is more preferably 85% or more. The upper limit of the transmittance may be 100%, but from the viewpoint of ease of manufacturing the photosensitive resin laminate, it may preferably be 99% or less. Means for adjusting the transmittance to 80% or more include, but are not limited to, ensuring that the photosensitive resin composition layer does not substantially contain coloring substances (dyes, pigments, etc.) or dyes that develop color upon exposure to light. (More specifically, the content of the coloring substance should be 0% by mass or more and less than 0.001% by mass based on the total solid content of the photosensitive resin composition layer), and the haze of the support film should be a value is 5 or less.

In the present disclosure, "after exposure" means a state after 10 minutes have elapsed after irradiation with a light amount of 500 mJ/cm ² unless otherwise specified.

In the present disclosure, a "colored substance" refers to a substance that absorbs in the visible range before or after exposure (specifically, a molar absorption coefficient of 420 to 800 nm when measured with a spectrophotometer is 10,000 L/(mol・cm). ) or more) means a substance.

Coloring substances include, for example, phthalocyanine green, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, Diamond Green, or a combination of a leuco dye or a fluoran dye and a halogen compound. Examples include dyes.
Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl)methane [leucomalachite green], and fluoran dyes. can be mentioned.

In one embodiment, the photosensitive resin laminate is for direct exposure. As a method for exposing photosensitive resins, there are known methods such as a direct writing method and a method using a mask, but the direct writing method is preferable because microchannels having a complicated shape can be formed with high dimensional accuracy. As for the characteristics of the photosensitive resin composition layer suitable for direct exposure, a photosensitive resin layer with high sensitivity is preferable. Generally, in the direct writing method, a large area is exposed by repeating or scanning a small exposure area using a digital micromirror device, a polygon mirror, or the like. At this time, since the exposure time per unit area is shortened in order to shorten the exposure tact, it is preferable that the photosensitive resin layer has high sensitivity. Examples of the highly sensitive photosensitive resin composition include a radical negative type photosensitive resin layer containing an alkali-soluble polymer, an addition polymerizable monomer, and a photopolymerization initiator. In such a negative photosensitive resin layer, radical polymerization, that is, curing reaction, is inhibited by oxygen in the air during exposure, so it is preferably covered with a plastic film that has low oxygen permeability and high transparency. . For these reasons, photosensitive resin laminates are preferably used for direct exposure.

In a preferred embodiment, the photosensitive resin composition layer is composed of a photosensitive resin composition having a ratio (I/O) of inorganic value (I) to organic value (O) of 1.0 or less. .
including.

The ratio (I/O) between the inorganic value (I) and the organic value (O) is also called the I/O value or the inorganic value/organic value, and is the ratio of the polarity of a member or compound from an organic concept. This is a type of functional group contribution method that sets parameters for each functional group.

Ratio (I/O) is the organic conceptual diagram (Yoshio Koda, Sankyo Publishing (1984)); KUMAMOTO PHARMACEUTICAL BULLETIN, No. 1, Sections 1-16 (1954); Chemistry, Volume 11, Vol. Detailed explanations can be found in literature such as No. 10, paragraphs 719-725 (1957). The ratio (I/O) roughly divides the properties of a member or compound into organic groups that exhibit covalent bonding properties and inorganic groups that express ionic bonding properties, and is calculated on orthogonal coordinates named organic and inorganic axes. Each point is positioned and shown.

The inorganicity value (I) is a numerical representation of the influence of various substituents or bonds of an organic compound on the boiling point, based on the hydroxyl group. Specifically, if the distance between the boiling point curve of a straight-chain alcohol and the boiling point curve of a straight-chain paraffin is taken around 5 carbon atoms, it will be approximately 100°C, so the influence of one hydroxyl group is determined as 100 numerically. The value obtained by quantifying the influence of various substituents or various bonds on the boiling point based on this numerical value is the inorganic value (I) of the substituent that the organic compound has. For example, the inorganic value (I) of the -COOH group is 150, and the inorganic value (I) of the double bond is 2. Therefore, the inorganic value (I) of a certain type of organic compound means the sum of the inorganic values (I) of various substituents, bonds, etc. that the compound has.

The organicity value (O) is determined based on the influence of the carbon atom representing the methylene group on the boiling point, using the methylene group in the molecule as a unit. In other words, since the average increase in boiling point due to the addition of one carbon to a linear saturated hydrocarbon compound with carbon numbers of 5 to 10 is 20°C, the organic value of one carbon atom is set to 20 based on this. Based on this, the organicity value (O) is a value that quantifies the influence of various substituents or bonds on the boiling point. For example, the organic value (O) of the nitro group (-NO ₂ ) is 70.

In general, the closer the ratio (I/O) is to 0, the more nonpolar (more hydrophobic, organic) it is, while the larger the value, the more polar (more hydrophilic, more inorganic) it is. Indicates that it is an organic substance. The ratio (I/O) of the photosensitive resin composition layer is preferably 1.0 or less, more preferably 0.0 from the viewpoint of the resistance (fluid resistance) of the photosensitive resin laminate to the fluid flowing through the microchannel. It is 9 or less, more preferably 0.8 or less, particularly preferably 0.7 or less. The ratio (I/O) is preferably 0.0 from the viewpoint of fluid resistance, but from the viewpoint of ease of manufacturing and developability of the photosensitive resin laminate, it is 0.1 or more, 0.2 or more, or 0. .3 or more. Note that the above ratio (I/O) is a value calculated based on the base resin and monomer of the photosensitive resin composition (that is, excluding the photopolymerization initiator and additives).

In a preferred embodiment, the photosensitive resin composition layer has an elastic modulus of 2 GPa or less after exposure. The elastic modulus is preferably 2 GPa or less, more preferably 1.5 GPa or less, even more preferably 1.0 GPa or less from the viewpoint of obtaining good crack resistance, and preferably 0.1 GPa or less from the viewpoint of obtaining good mechanical strength. Above, it is more preferably 0.3 GPa or more, still more preferably 0.5 GPa or more.

In a preferred embodiment, the photosensitive resin composition layer has an elongation at break of 30% or more after exposure. The elongation at break is preferably 30% or more, more preferably 60% or more, even more preferably 100% or more from the viewpoint of obtaining good crack resistance, and preferably 300% or less from the viewpoint of obtaining good mechanical strength. , more preferably 200% or less, still more preferably 180% or less.

In a particularly preferred embodiment, the photosensitive resin composition layer has an elastic modulus of 2 GPa or less and an elongation at break of 30% or more after exposure.

The constituent elements of the photosensitive resin laminate for a microchannel device according to this embodiment will be described below.

<Photosensitive resin composition layer>
The photosensitive resin composition layer can be formed by applying a photosensitive resin composition onto a support film, drying it, and laminating the layers. The photosensitive resin composition may contain any polymer and/or monomer as long as it can impart photosensitivity to the photosensitive resin laminate, and may further contain a photopolymerization initiator, other additives, etc., if desired. That's fine.

The photosensitive resin composition contains (a) a carboxyl group from the viewpoint of formability of a member for a microchannel device by photolithography, laminateability between a photosensitive resin laminate and a base material of a microchannel device, etc. It is preferable to include an alkali-soluble polymer, (b) an addition polymerizable monomer, and (c) a photopolymerization initiator. The photosensitive resin composition may also contain an epoxy resin such as EPON® SU-8 type resin, bisphenol A novolak epoxy resin, etc., as long as it can be used to form the photosensitive resin composition layer into a film.

(a) Alkali-soluble polymer containing a carboxyl group (a) Alkali-soluble polymer containing a carboxyl group has an α,β-unsaturated carboxyl group-containing monomer as a polymerization component, and the alkali-soluble polymer contains an alkali-soluble polymer. It is preferable that the equivalent weight is 100 to 600 and the weight average molecular weight is 5,000 to 500,000. The carboxyl group in the alkali-soluble polymer containing a carboxyl group is necessary for the photosensitive resin composition to have developability or strippability with respect to a developer or stripper consisting of an aqueous alkaline solution. Acid equivalent refers to the mass of an alkali-soluble polymer having one equivalent of carboxyl group therein. A more preferable lower limit of the acid equivalent is 250, and a more preferable upper limit is 450. (a) The acid equivalent of the alkali-soluble polymer containing a carboxyl group improves development resistance, resolution, and cured product of the photosensitive resin composition layer (also referred to as "cured resist film" in this disclosure), etc. It is preferably 100 or more from the viewpoint of improving adhesion with the member and also ensuring compatibility with the solvent or other components in the photosensitive resin composition, especially with the addition polymerizable monomer (b) described below. From the viewpoint of improving developability and removability, it is preferably 600 or less. The acid equivalent is measured by potentiometric titration using 0.1 mol/L sodium hydroxide using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.

(a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group is preferably 5,000 to 500,000. The weight average molecular weight is determined from the viewpoint of improving the fluid resistance of the photosensitive resin laminate, from the viewpoint of suppressing the incorporation of air into the microchannel during lamination, and from the viewpoint of making the thickness of the photosensitive resin laminate uniform and resistant to developing solutions. The average molecular weight is preferably 5,000 or more from the viewpoint of obtaining the same, and 500,000 or less from the viewpoint of maintaining developability. In order to achieve both fluid resistance and developability, the lower limit of the weight average molecular weight of (a) the alkali-soluble polymer containing a carboxyl group is more preferably 20,000 or more or 40,000 or more; The upper limit value is more preferably 250,000 or less, 200,000 or less, 150,000 or less, or 100,000 or less.

The weight average molecular weight in this specification means the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of polystyrene (Shodex STANDARD SM-105, manufactured by Showa Denko KK). (a) The weight average molecular weight of the alkali-soluble polymer containing a carboxyl group can be measured using gel permeation chromatography manufactured by JASCO Corporation under the following conditions:
Differential refractometer: RI-1530
Pump: PU-1580
Degasser: DG-980-50
Column oven: CO-1560
Column: KF-8025, KF-806M x 2, KF-807 in order
Eluent: THF.

(a) The alkali-soluble polymer containing a carboxyl group is preferably a (co)polymer containing as a component one or more monomers selected from the first or second monomers described below. .

The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred from the viewpoint of alkali developability.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in its molecule. For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, Vinyl alcohol esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, and vinyl acetate; ) acrylonitrile, styrene, and polymerizable styrene derivatives. Among them, from the viewpoint of resolution of microchannel patterns, methyl (meth)acrylate, n-butyl (meth)acrylate, styrene, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and benzyl (meth)acrylate At least one selected from the group consisting of is preferred, and styrene is more preferred.

In this specification, "(meth)acrylic" means "acrylic" and its corresponding "methacrylic", and "(meth)acrylate" means "acrylate" and its corresponding "methacrylate". and "(meth)acryloyl" means "acryloyl" and its corresponding "methacryloyl."

(a) The alkali-soluble polymer containing a carboxyl group is prepared by mixing the above monomers and adding a radical polymerization initiator such as benzoyl peroxide to a solution diluted with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It can be synthesized by adding an appropriate amount of azoisobutyronitrile and heating and stirring. In some cases, synthesis may be carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, a solvent may be further added to the reactant to adjust the concentration to a desired level. As a synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

(a) In the alkali-soluble polymer containing a carboxyl group, the copolymerization ratio of the first monomer and the second monomer is such that the first monomer is 10 to 60% by mass and the second monomer is 10 to 60% by mass. It is preferable that the amount of monomer is 40 to 90% by weight, more preferably 15 to 35% by weight of the first monomer and 65 to 85% by weight of the second monomer.

(a) More specific examples of alkali-soluble polymers containing carboxyl groups include methyl methacrylate, polymers containing methacrylic acid and styrene as copolymer components, methyl methacrylate, methacrylic acid, and n-butyl methacrylate. A polymer containing as a copolymerization component, a polymer containing methacrylic acid, benzyl methacrylate, and styrene as a copolymerization component, a polymer containing methacrylic acid and benzyl methacrylate as a copolymerization component, methacrylic acid, 2-ethylhexyl acrylate, Examples include polymers containing 2-hydroxyethyl methacrylate and styrene as copolymer components.

The content of (a) alkali-soluble polymer containing a carboxyl group in the photosensitive resin composition is preferably 20 to 90% by mass, more preferably 40 to 60% by mass, based on the total solid content of the photosensitive resin composition. It is within the range of mass%. (a) The content of the alkali-soluble polymer containing a carboxyl group is preferably 20% by mass or more from the viewpoint of maintaining the resistance of the photosensitive resin composition in photolithography, and the content of the alkali-soluble polymer containing a carboxyl group is preferably 20% by mass or more, and From the viewpoint that the subsequent resist pattern has flexibility, it is preferably 90% by mass or less.

(b) Addition polymerizable monomer (b) Addition polymerizable monomer is a compound having at least one polymerizable ethylenically unsaturated bond in the molecule. The ethylenically unsaturated bond is preferably a terminal ethylenically unsaturated group.
From the viewpoint of development speed, the addition polymerizable monomer (b) preferably contains a monomer having a structure represented by (Formula I) and a molecular weight of 200 to 600 in an amount of 50% by mass in the addition polymerizable monomer (b). More preferably, it is contained in an amount of 60% by mass, still more preferably 70% by mass or more, particularly preferably 100% by mass.
C-((CH ₂ )R ¹ )((CH ₂ )R ² )((CH ₂ )R ³ )((CH ₂ )R ⁴ )
...(Formula I)
Here, R ¹ to R ⁴ refer to monovalent organic groups.

A monovalent organic group is a group bonded to the -CH ₂ - group in (Formula I) by a -C, -N, -O, -S, or -P bond. A saturated aliphatic hydrocarbon group is present in the monovalent organic group that is not bonded to the -CH ₂ - group in (Formula I) in the -C, -N, -O, -S, or -P bond. , unsaturated aliphatic hydrocarbon group, aromatic group, heterocyclic group, ether group, ester group, amide group, imide group, amino group, urethane group, sulfone group, halogen, alkylene oxide group, (meth)acryloyl group, It can contain carboxyl groups, hydroxyl groups, etc. In particular, a (meth)acryloyl group, a carboxyl group, a hydroxyl group, etc. are bonded to the -CH ₂ - group in (Formula I) through an ethylene oxide group, a propylene oxide group, a butylene oxide group, or any of these. A structure in which Further, the monovalent organic group may have a polyalkylene oxide chain. Examples of the alkylene oxide constituting the polyalkylene oxide chain include polyethylene oxide and polypropylene oxide.

Further, the monomer having the structure of (Formula I) preferably has a molecular weight of 200 or more from the viewpoint of staining after development and 600 or less from the viewpoint of development speed.
Examples include trimethylolpropane triacrylate (molecular weight 296), trimethylolpropane EO-modified triacrylate (e.g. 3 mole EO modified product, molecular weight 428), trimethylolpropane trimethacrylate (molecular weight 338), pentaerythritol tetraacrylate (molecular weight 352). , pentaerythritol triacrylate (molecular weight 284), pentaerythritol tetramethacrylate (molecular weight 408), pentaerythritol EO modified tetramethacrylate (e.g. 4 mol modified form of EO, molecular weight 584), pentaerythritol EO modified tetraacrylate (e.g. 4 molar EO modified form) , molecular weight 528), and the like.

In addition, from the viewpoint of the high resolution of the microchannel pattern and the shape of the partition walls, (b) addition polymerizable monomers include bisphenol A-based (meth)acrylate compounds, polyfunctional monomers, monomers having repeating units of alkylene oxide, It is preferable to use at least one selected from the group consisting of cyclic monomers and aromatic monomers.

In this specification, a bisphenol A-based (meth)acrylate compound refers to a (meth)acryloyl group or a carbon-carbon unsaturated double bond derived from a (meth)acryloyl group and -C ₆ H ₄ - derived from bisphenol A. Refers to a compound having a C(CH ₃ ) ₂ -C ₆ H ₄ - group. Specific examples include polyethylene glycol dimethacrylate (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.) in which ethylene oxide is added to each end of bisphenol A in an average of 2 molar units, or bisphenol A is added to both ends of bisphenol A in an average of 5 molar units each. Dimethacrylate of polyethylene glycol to which molar units of ethylene oxide has been added (NK Ester BPE-500 manufactured by Shin Nakamura Chemical Co., Ltd.), ethylene oxide with an average of 6 molar units and propylene oxide with an average of 2 molar units at both ends of bisphenol A. Examples include polyalkylene glycol dimethacrylate to which is added, and polyalkylene glycol dimethacrylate to which an average of 15 mol units of ethylene oxide and an average of 2 mol units of propylene oxide are added to both ends of bisphenol A.

Examples of (b) addition polymerizable monomers other than bisphenol A-based (meth)acrylate compounds include 4-nonylphenylheptaethylene glycol dipropylene glycol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, phenoxyhexaethylene glycol acrylate, A reaction product of a half ester compound of phthalic anhydride and 2-hydroxypropyl acrylate and propylene oxide (manufactured by Nippon Shokubai Chemical, trade name OE-A200), polypropylene glycol to which an average of 12 moles of propylene oxide has been added is further added with ethylene oxide. Dimethacrylate of glycol with an average of 3 moles added to each end, dimethacrylate of polybutylene glycol with an average of 28 moles of butylene oxide added to each end;
4-n-octylphenoxypentapropylene glycol acrylate, 1,6-hexanediol (meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. Polyoxyalkylene glycol di(meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, glycerol tri(meth)acrylate, tri, tetra or penta(meth)acrylate of pentaerythritol, trimethylolpropane tri Glycidyl ether tri(meth)acrylate;
2,2-bis(4-(meth)acryloxypentaethoxyphenyl)propane, 2,2-bis(4-((meth)acryloxypentaethoxy)cyclohexyl)propane;
A polyfunctional (meth)acrylate containing a urethane group such as a urethane of hexamethylene diisocyanate and nonapropylene glycol monomethacrylate, a polyurethane synthesized from polybutylene glycol to which an average of 28 moles of butylene oxide has been added and hexamethylene diamine. Examples include dimethacrylate of diol, polyfunctional (meth)acrylate of isocyanuric acid ester compound, and the like. These may be used alone or in combination of two or more types, and may also be used in combination with a bisphenol A-based (meth)acrylate compound.

The content of the addition polymerizable monomer (b) in the photosensitive resin composition is preferably 5 to 75% by mass, more preferably 15 to 70% by mass, and more preferably 15 to 70% by mass, based on the total solid content of the photosensitive resin composition. It is preferably within the range of 20 to 55% by mass. (b) The content of the addition polymerizable monomer is preferably 5% by mass or more from the viewpoint of resolution and adhesion between the cured resist film and other members, and from the viewpoint of flexibility of the cured resist film. It is preferably 75% by mass or less.

(c) Photopolymerization initiator (c) As the photopolymerization initiator, those commonly used as photopolymerization initiators for photosensitive resins can be appropriately used. For example, hexaarylbisimidazole (hereinafter also referred to as triarylimidazolyl dimer) can be used.

Examples of the triarylimidazolyl dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer (hereinafter referred to as "2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetraphenyl-1,1'-bisimidazole"), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5 '-diphenylimidazolyl dimer, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylimidazolyl dimer;
2,4,5-tris-(o-chlorophenyl)-diphenylimidazolyl dimer, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-imidazolyl dimer, 2, 2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3-difluoromethyl phenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,4-difluorophenyl)-4,4',5, 5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer;
2,2'-bis-(2,5-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2, 6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3,4-trifluorophenyl)-4 , 4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5 '-tetrakis-(3-methoxyphenyl)-imidazolyl dimer;
2,2'-bis-(2,3,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis- (2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'-bis-(2,4,6- trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer;
2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, 2,2'- bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer, and 2,2'-bis-(2 , 3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-imidazolyl dimer.

Among these, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer is preferred because it has a high effect on resolution and strength of the cured resist film. These may be used alone or in combination of two or more, and may also be used in combination with acridine compounds, pyrazoline compounds, etc. described below.

(c) As a photopolymerization initiator, an acridine compound or a pyrazoline compound can also be used. Examples of acridine compounds include acridine, 9-phenylacridine, 9-(4-tolyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-hydroxyphenyl)acridine, 9-ethyl acridine, 9-chloroethyl Acridine, 9-methoxyacridine, 9-ethoxyacridine;
9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert -butylphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-(4-acetylphenyl)acridine, 9-(4-dimethylaminophenyl)acridine, 9-(4-chlorophenyl)acridine;
9-(4-bromophenyl)acridine, 9-(3-methylphenyl)acridine, 9-(3-tert-butylphenyl)acridine, 9-(3-acetylphenyl)acridine, 9-(3-dimethylaminophenyl) ) acridine, 9-(3-diethylaminophenyl)acridine, 9-(3-chlorophenyl)acridine, 9-(3-bromophenyl)acridine, 9-(2-pyridyl)acridine, 9-(3-pyridyl)acridine, 9-(4-pyridyl)acridine is mentioned. Among these, 9-phenylacridine is preferred.
The acridine compound is preferably used in combination with a halogen compound from the viewpoint of curability of the photosensitive resin layer after exposure. Halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3 -dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, chlorinated triazine compounds, and the like. Among them, tribromomethylphenylsulfone is preferred from the viewpoint of curability.

Examples of pyrazoline compounds include 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-(4-(benzoxazol-2-yl)phenyl) -3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline is preferred.

Examples of other photopolymerization initiators include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, and 1-chloroanthraquinone. , quinones such as 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone;
Aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], and 4,4'-bis(diethylamino)benzophenone, benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethyl Benzoin ethers such as benzoin;
Benzyl dimethyl ketal, benzyl diethyl ketal, combination of thioxanthone and alkylaminobenzoic acid, 1-phenyl-1,2-propanedione-2-O-benzoin oxime, 1-phenyl-1,2-propanedione-2-( Examples include oxime esters such as (O-ethoxycarbonyl) oxime.
Oxime compounds are preferred when colorless transparency of the microchannel is required or from the viewpoint of suppressing fluorescence to facilitate detection of luminescent signals of the microchannel device. Examples include Irgacure OXE01 and Irgacure OXE02 manufactured by BASF Japan Co., Ltd., and ADEKA Arkles NCI-831 manufactured by ADEKA Co., Ltd.

In addition, examples of the above-mentioned combinations of thioxanthone and alkylaminobenzoic acid include a combination of ethylthioxanthone and ethyl dimethylaminobenzoate, a combination of 2-chlorothioxanthone and ethyl dimethylaminobenzoate, and a combination of isopropylthioxanthone and dimethylaminobenzoate. A combination with ethyl acid may be mentioned. Additionally, N-aryl amino acids may be used. Examples of N-arylamino acids include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, and the like. Among them, N-phenylglycine is particularly preferred.

The content of the photopolymerization initiator (c) in the photosensitive resin composition is preferably in the range of 0.01 to 30% by mass, based on the total solid content of the photosensitive resin composition, and the lower limit is more preferable. The value is 0.05% by mass or more, a more preferred lower limit is 0.1% by mass or more, a more preferred upper limit is 15% by mass or less, and an even more preferred upper limit is 10% by mass or less. (c) The content of the photopolymerization initiator is preferably 0.01% by mass or more from the viewpoint of obtaining sufficient sensitivity during photopolymerization by exposure. The content is preferably 30% by mass or less from the viewpoint of sufficiently transmitting light even to parts far away from the surface of the film and obtaining good resolution and good adhesion between the cured resist film and other members.

(d) Other additives The photosensitive resin composition may contain various additives in addition to the components (a) to (c) above.

For example, in order to improve the thermal stability and storage stability of the photosensitive resin composition, at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, and hindered phenolic antioxidants is used. It is preferable that the photosensitive resin composition contains one or more kinds of compounds.

Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, and 2,2'-methylenebis. (4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, Bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole are mentioned.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, (N,N-dibutylamino)carboxybenzotriazole, N-( N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-ethylhexyl)amino Ethylenecarboxybenzotriazole is mentioned.

Examples of hindered phenolic antioxidants include the IRGANOX series manufactured by BASF Japan, and the ADEKA STAB (AO) series manufactured by ADEKA.

The total amount of the radical polymerization inhibitor, benzotriazole, carboxybenzotriazole, and/or hindered phenol antioxidant is preferably 0.001 to 3 mass based on the total solid content of the photosensitive resin composition. %, a more preferable lower limit is 0.05% by mass or more, and a more preferable upper limit is 1% by mass or less. The total amount added is preferably 0.001% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and preferably 3% by mass or less from the viewpoint of maintaining sensitivity.

The photosensitive resin composition may contain a plasticizer, if necessary. Examples of the plasticizer include compounds obtained by modifying bisphenol A with polyalkylene oxide. In addition, for example, sorbitan derivatives such as polyoxyethylene sorbitan laurate and polyoxyethylene sorbitan oleate, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, phthalic acid esters such as diethyl phthalate, and o-toluenesulfonic acid amide. , p-toluenesulfonamide, tributyl citrate, triethyl citrate, triethyl acetyl citrate, tri-n-propyl acetyl citrate, tri-n-butyl acetyl citrate, and the like can be used. In particular, it is preferable to use sorbitan derivatives and polyalkylene glycols.

The content of the plasticizer in the photosensitive resin composition is preferably 1 to 50% by mass, based on the total solid content of the photosensitive resin composition, with a more preferred lower limit of 3% by mass and a more preferred upper limit of 3% by mass. It is 30% by mass. From the viewpoint of suppressing the delay in development time and imparting flexibility to the cured film, the content is preferably 1% by mass or more, and from the viewpoint of suppressing insufficient curing, the content is preferably 50% by mass or less.

In one embodiment, the thickness of the photosensitive resin composition layer is preferably 100 μm or more, more preferably 120 μm or more, even more preferably 240 μm or more, and preferably 720 μm or less, more preferably 480 μm or less.

The development time per 25 μm of thickness of the photosensitive resin composition layer using a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. is preferably 15 to 50 seconds/25 μm, more preferably 20 to 40 seconds/25 μm, More preferably, it is 25 to 35 seconds/25 μm. The above development time is as shown below. First, a photosensitive resin laminate having a photosensitive resin layer thickness of 25 μm is produced by the method described in Example <Preparation of photosensitive resin laminate 2> of the present specification. Next, a copper-clad laminate with a thickness of 1.2 mm, a copper foil of 35 μm, a length of 150 mm, and a width of 250 mm was coated with a normal pressure laminator (VA-400III manufactured by Taisei Laminator Co., Ltd.) at a speed of 0.2 m/min and a cylinder pressure of 0. Laminate at .2 MPa and roll temperature of 70°C. After peeling off the support film, development is performed using a 1% by mass aqueous sodium carbonate solution at 30° C. using a conveyor-type spray developing machine, and the minimum time required for removing the photosensitive resin composition layer is defined as the development time.

<Support film>
The support film supports the photosensitive resin composition layer in the form of a film. The support film is preferably one that transmits light with wavelengths of 510 nm and 600 nm and light emitted from the exposure light source. Such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, and polystyrene. films, polyacrylonitrile films, styrene copolymer films, polyamide films, cellulose derivative films, etc. These films may be stretched if necessary. From the viewpoint of resolution, a film with a haze value of 5 or less is preferred. A haze value of 3 or less is more preferable, a haze value of 2.5 or less is even more preferable, and a haze value of 1 or less is even more preferable. As for the thickness of the support film, the thinner it is, the more advantageous it is in terms of image formation and economic efficiency. From the viewpoint of reducing the thickness, those with a diameter of 10 to 30 μm are preferably used. For example, GR-19 and GR-16 manufactured by Teijin Films Co., Ltd., R310-16 and R340G16 manufactured by Mitsubishi Plastics Co., Ltd., and FB40 (16 μm film thickness) and FB60 (16 μm film thickness) manufactured by Toray Polyester Film Co., Ltd. I can list them.

In one embodiment, the adhesion strength between the support film and the photosensitive resin composition layer is 3 gf/inch or more from the viewpoint of easy handling without peeling when the photosensitive resin laminate is slit or laminated onto a substrate. It is. In addition, from the viewpoint of suppressing the occurrence of peeling lines when peeling the support film after exposure, it is 100 gf/inch or less, preferably 80 gf/inch or less, more preferably 50 gf/inch or less, and even more preferably 30 gf/inch or less. It is. For example, increasing the ratio of the alkali-soluble polymer in the photosensitive resin composition, increasing the weight average molecular weight of the alkali-soluble polymer, increasing the composition ratio of the first monomer in the alkali-soluble resin, The adhesion strength can be designed to be low by, for example, reducing the proportion of an addition polymerizable monomer having a relatively low viscosity in the photosensitive resin composition.
The peel line is a minute difference in level on the surface of the photosensitive resin composition layer after the support film is peeled off, which occurs when the adhesion between the support film and the photosensitive resin composition layer is excessively high. Usually, peeling lines occur in a direction substantially perpendicular to the peeling direction. Peeling lines can cause non-uniformity in the film thickness of the photosensitive resin composition layer, which can lead to non-uniformity in the volume of the fluid held in the microchannel, so it is important to suppress the occurrence of peeling lines. desirable. The adhesion strength is a value measured under the conditions described in the [Examples] section of the present disclosure (ie, a value at a peel angle of 180 degrees).

In addition, in one aspect, it is preferable that the photosensitive resin laminate of this embodiment is combined with a protective film. In one embodiment, a protective film may be disposed on the photosensitive resin composition layer. The protective film may be any film as long as it has a smaller adhesion to the photosensitive resin composition layer than the support film and is removable. For example, polyethylene film, polypropylene film, stretched polypropylene film, etc. can be used as the protective film. Further, for example, a film with excellent releasability disclosed in Japanese Patent Application Laid-Open No. 59-202457 can be used. The protective film is preferably a polypropylene film or a release-treated plastic film from the viewpoint of good releasability and from the viewpoint of being peeled off from the photosensitive resin laminate during formation of the microchannel device.

The thickness of the protective film is preferably 10 to 100 μm, more preferably 10 to 50 μm, from the viewpoint of the thickness and dimensional stability of the laminate of the photosensitive resin laminate and the protective film. Specific examples of the protective film include release-treated PET film 25X (thickness: 25 μm) manufactured by Lintec Corporation, and GF-18, GF-818, and GF-858 manufactured by Tamapori Corporation.

<Method for manufacturing photosensitive resin laminate>
As a method for manufacturing the photosensitive resin laminate, known methods can be employed. For example, the photosensitive resin composition constituting the photosensitive resin composition layer is mixed with a solvent to prepare a photosensitive resin composition formulation, and then applied to the support film using a bar coater or a roll coater. It can be obtained by drying and laminating a photosensitive resin composition layer made of the photosensitive resin composition on a support film. If desired, a protective film may be further laminated on the photosensitive resin composition layer.

The photosensitive resin composition preparation is preferably prepared by adding a solvent so that the viscosity at 25° C. is 500 to 4000 mPa·sec. Examples of solvents include methyl ethyl ketone, acetone, ethanol, methanol, propanol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, etc., which are used to control the viscosity, drying properties, residual solvent amount, coating properties, and foaming of the photosensitive resin composition formulation. They can be appropriately selected and used from the viewpoint of gender.

The photosensitive resin laminate can be optionally laminated with a protective film, wound up around a core, and used in the form of a roll. In addition, the photosensitive resin laminate can be covered with a light-shielding sheet such as a polyethylene film from the viewpoint of suppressing adhesion of foreign substances and exposure to light during storage or transportation.

[Microchannel device and its manufacturing method]
The photosensitive resin laminate for microchannel devices of this embodiment is used as a member of various microchannel devices such as POCT (Point of Care Testing) kits, ELISA (Enzyme-Linked ImmunoSorbent Assay) devices, and microreactors. can. In one aspect, the microchannel device includes a base material having a surface formed with a microchannel through which a fluid (liquid or gas) passes, a lid member disposed to cover the microchannel, and a lid member disposed to cover the microchannel. It includes an introduction part that introduces the fluid into the microchannel, and a discharge part that discharges the fluid from the microchannel. The base material may be an inorganic (eg, silicon, glass, carbon material, etc.) or organic (eg, various polymers) material. In one embodiment, fluid may be delivered to the desired location of the device by a pump, centrifugal force, or the like. In one embodiment, the microchannel is formed by a partition material disposed on a base material (for example, a partition material that is a hardened resist film formed on the base material by photolithography). In one embodiment, the microchannel is formed by cutting grooves on the surface of the base material.

In a typical embodiment, the photosensitive resin laminate of this embodiment is included in a microchannel device as a permanent film after exposure. In one embodiment, after exposure of the photosensitive resin composition layer, the support film is removed and only the cured resist film is included within the microchannel device. In another embodiment, the support film is not removed after exposure of the photosensitive resin composition layer, and the support film and cured resist film are included within the microchannel device.

The size of the microchannel is selected depending on the purpose, and may be, for example, a width of 1 to 1000 μm, or 1 to 100 μm, or 10 to 70 μm, and a depth of 1 to 50 μm, or 5 to 30 μm. In one aspect, the bottom and side surfaces of the microchannel may both be flat, and the angle formed by these may be approximately right angles; however, the shape of the microchannel is not limited to this, and may be designed according to the purpose. It's okay to be.

According to the photosensitive resin laminate according to this embodiment, a member having a complicated shape can be formed with excellent dimensional accuracy and good fluid resistance and crack resistance. Therefore, the photosensitive resin laminate according to this embodiment is particularly useful as a partition material for microchannels. In particular, in devices configured to deliver fluid to a desired position using centrifugal force (for example, see also the above-mentioned Patent Document 1 (Japanese Patent Application Laid-open No. 2017-122618)), microflow Since the shape of the channel tends to be complicated, the photosensitive resin laminate according to this embodiment can be particularly suitably applied to the partition material of the microchannel in such a device. Furthermore, the photosensitive resin laminate according to this embodiment can be advantageously applied to a lid material for a microchannel due to its good fluid resistance and crack resistance. In any application, the good detectability during fluorescence detection obtained by the photosensitive resin laminate according to the present embodiment is advantageous for highly accurate detection of a target substance.

The method for manufacturing a microchannel device is not particularly limited, and for example, a method including the steps of forming a microchannel on a base material and sealing the microchannel by laminating a lid material on the microchannel. It can be manufactured by For example, when the photosensitive resin laminate of this embodiment is used as a partition material and a lid material, the microchannel device may be, for example,
a microchannel forming step of laminating a photosensitive resin laminate on a base material, and forming a cured resist film as a partition material of the microchannel by pattern exposure and development of the photosensitive resin composition layer;
a microchannel sealing step of laminating a photosensitive resin laminate on at least the partition material so as to cover the microchannel, and forming a hardened resist film as a cover material for the microchannel by exposing the entire surface to light;
It can be manufactured by a method including

In the microchannel forming step, the photosensitive resin laminate is laminated onto the substrate with the photosensitive resin composition layer side facing the substrate, and exposed to light in a pattern corresponding to the desired shape of the partition wall material. (preferably direct exposure), further removing the support film, and developing to form a plurality of partition wall materials that define microchannels and are composed of hardened resist films.

Next, in the microchannel sealing step, the photosensitive resin laminate is laminated on at least the partition material so as to cover the microchannel, with the photosensitive resin composition layer side facing the partition material, and the entire surface is exposed to light. Typically, a lid material made of a support film and a cured resist film is formed without removing the support film.

From the viewpoint of forming a cured resist film with good dimensional accuracy, lamination of the photosensitive resin laminate is preferably carried out under reduced pressure, more preferably at a vacuum degree of 30 to 70 Pa, and even more preferably at a vacuum degree of 40 to 60 Pa.

When forming a cured resist film with a multi-layer structure, lamination, exposure and development of a single-layer photosensitive resin composition layer may be repeated multiple times. A post-batch exposure may also be performed. Bulk exposure is preferable in that it is possible to form a cured resist film with excellent dimensional accuracy (that is, with little misalignment between layers).

The photosensitive resin laminate according to this embodiment is particularly suitably applied to a partition material and/or a lid material of a compact disk (CD) type microchannel device for ELISA. An example of the configuration of a CD-type ELISA device will be described below.

In the CD-type ELISA device according to the exemplary embodiment, a liquid tank for storing a liquid substance and an analysis part for detecting, reacting, adsorbing, desorbing or decomposing the liquid substance are provided on a disk-shaped substrate (as a base material). A microchannel is formed to connect the liquid tank and the analysis section and allow a liquid to flow between them, and the microchannel is sealed with a lid material. In an exemplary embodiment, the substrate diameter is about 10 cm, the minimum width of the microchannel is about 45 μm, and the depth of the microchannel is about 30 μm. The number of analysis parts on the substrate is, for example, 4 to 20 or 14 to 16. The liquid is sent radially outward from the center using centrifugal force due to the rotation of the substrate, and is supplied to each analysis section from the liquid tank via the microchannel.

The substrate may be made of either a light-transmitting material or a non-light-transmitting material, preferably a light-transmitting material such as resin or glass, and more preferably a resin. Note that "translucent" is broadly interpreted to mean that light can be transmitted, regardless of whether it is colored or colorless, and regardless of the amount of light transmittance.

As resins constituting the substrate, acrylic resins, polypropylene, polycarbonate resins, cycloolefin resins, polystyrene resins, polyester resins, urethane resins, vinyl chloride resins, and silicone resins are suitable for forming microchannels. , fluororesin, etc.

In an exemplary embodiment, a method of manufacturing a CD-type ELISA device includes the following steps:
(1) Step of forming a plurality of partition walls on a substrate to form a microchannel;
(2) Providing a through hole in the substrate;
(3) Step of fitting the analysis section through the through hole from the back side of the substrate;
(4) Step of laminating the lid material from the front side of the substrate;
(5) If desired, the step of partially cutting the substrate on which the microchannel is formed to adjust the outer shape; and (6) If desired, the step of cleaning the partition wall;
including. The order of each process can be freely changed depending on the efficiency of the manufacturing process.

When step (1) is carried out by photolithography, the protective film (if any (case) is peeled off, the support film is maintained and laminated to the substrate, exposed and developed, and then the support film is removed to form a plurality of barrier rib materials that define microchannels.

When step (4) is performed by photolithography, the photosensitive resin laminate (if the photosensitive resin laminate of this embodiment is used for a lid material, this photosensitive resin laminate) is laminated on the substrate. , it can be cured by exposure to light to form a permanent film consisting of a support film and a cured resist film. Specifically, the protective film (if any) is peeled off from the photosensitive resin laminate, the support film is maintained, and the support film, photosensitive resin composition layer, CD-type ELISA device substrate, and CD-type ELISA device analysis are performed. Lamination can be carried out at a speed of about 0.18 m/min using a biaxial roll in a laminating order using a jig such that the surface irregularities of the ELISA substrate are aligned on one plane. The aforementioned jig is preferably made of a material that has low adhesion to the resist even during lamination, such as Teflon (registered trademark).

Examples of embodiments of the present invention will be specifically described below.
First, a method for producing evaluation samples of Examples and Comparative Examples will be explained, and then, an evaluation method and evaluation results for the obtained samples will be shown. Tables 1 to 3 show the names of the material components in the photosensitive resin composition formulation, the amounts blended in the resin composition formulation (parts by mass based on solid content), and some of the evaluation results.

[Preparation of evaluation sample]
Evaluation samples in Examples and Comparative Examples were prepared as follows.
<Preparation of photosensitive resin laminate 1>
A photosensitive resin composition having the composition shown in Example 1 and Example 6 in Table 1 below (however, the number for each component indicates the amount (parts by mass) of each component) and ethanol as a solvent were added and stirred thoroughly. and mixed to obtain a photosensitive resin composition preparation, and uniformly coated on the surface of a 16 μm thick polyethylene terephthalate film (FB40, manufactured by Toray Industries, Inc.) as a support using a bar coater, dried, and the photosensitive resin A composition layer was formed to obtain a photosensitive resin laminate. The thickness of the photosensitive resin composition layer was 240 μm. The amount of solvent remaining in the photosensitive resin composition layer was 1.5% by mass.
Next, GF-18 manufactured by Tamapori Co., Ltd. was laminated as a protective film on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated.

<Preparation of photosensitive resin laminate 2>
Photosensitive resin compositions having the compositions shown in Examples 2 to 5 and Comparative Examples 1 and 2 in Table 1 below (however, the numbers for each component indicate the amount (parts by mass) as solid content) and ethanol as a solvent were used. The photosensitive resin composition was added and thoroughly stirred and mixed to obtain a photosensitive resin composition preparation, which was uniformly coated on the surface of a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB40) as a support using a bar coater at 95°C. was dried for 5 minutes to form a photosensitive resin composition layer to obtain a photosensitive resin laminate. The thickness of the photosensitive resin composition layer was 25 μm.
Next, GF-818 manufactured by Tamapori Co., Ltd. was laminated as a protective film on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated.

<Preparation of photosensitive resin laminate 3>
Photosensitive resin compositions having the compositions shown in Examples 1 to 5 and Comparative Examples 1 and 2 in Table 1 below (however, the numbers for each component indicate the amount (parts by mass) as solid content) and ethanol as a solvent were used. The photosensitive resin composition was added and thoroughly stirred and mixed to obtain a photosensitive resin composition preparation, which was uniformly coated on the surface of a 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB40) as a support using a bar coater at 95°C. was dried for 5 minutes to form a photosensitive resin composition layer to obtain a photosensitive resin laminate. The thickness of the photosensitive resin composition layer was 5 μm. Next, GF-18 manufactured by Tamapori Co., Ltd. was laminated as a protective film on the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated.

[evaluation]
1. Calculation of ratio (I/O) Based on the composition shown in Table 1, the photosensitive resin composition according to each example is calculated from the inorganic value (I) and organic value (O) of the base resin (B) and monomer (M). The ratio of substances (I/O) was calculated as follows.
First, for each base resin (B), calculate the inorganic value (I) based on the organic conceptual diagram and multiply it by the blending amount (mass) shown in Table 1 to calculate the B _{(I x blending amount)} value. Then, the organic value (O) is calculated and multiplied by the blended amount to calculate the B _{(O x blended amount)} value.
Similarly, for each monomer (M), the inorganicity value (I) is calculated based on the organic conceptual diagram and multiplied by the blending amount shown in Table 1 to calculate the M _{(I x blending amount)} value, and The organic value (O) is calculated and multiplied by the blended amount to calculate the M _{(O x blended amount)} value.
The total value of B _{(I × blending amount)} of all base resins (B) and the total value of M _{(I × blending amount)} of all monomers (M) are added to obtain the total value I _{(B + M).} .
Add up the total value of B _{(O x blending amount)} of all base resins (B) and the total value of M _{(O x blending amount)} of all monomers (M) to obtain the total value O _{(B + M).} .
I _(B+M) is divided by O _(B+M) to calculate I _(B+M) /O _(B+M) , which is the ratio (I/O).

2. Measurement of transmittance The photosensitive resin laminate obtained in the above <Preparation of photosensitive resin laminate 3> with the protective film laminated thereon was exposed to 500 mJ/cm ² using an exposure machine HMW-201KB manufactured by Oak Seisakusho Co., Ltd. After 10 minutes of exposure, the protective film was peeled off, and the transmittance was measured using a spectrophotometer U-3010 manufactured by Hitachi High-Tech Science Co., Ltd. The analysis was conducted in a state where the support film and the photosensitive resin composition layer were laminated, and measurement was performed in a state where the analytical light was incident from the photosensitive resin composition layer side.

3. Measurement of elastic modulus The photosensitive resin laminate obtained in the above <Preparation of photosensitive resin laminate 2> with the protective film laminated thereon was exposed to 500 mJ/cm ² using an exposure machine HMW-201KB manufactured by Oak Seisakusho Co., Ltd. After exposure and peeling off the protective film, development was performed for twice the minimum development time to prepare a test piece measuring 5 cm in length and 5 mm in width. The test piece was stored for one day in an environment of 23° C. and 50% relative humidity while being peeled from the support film. A tensile test was performed on the test piece using a tensile tester Tensilon RTM-500 manufactured by A&D Co., Ltd. at a tensile speed of 100 mm/min. The elastic modulus of the cured product of the photosensitive resin composition layer was determined from the initial slope of the obtained stress-strain curve. The elongation at which the test piece broke was determined as the elongation of the test piece.

4. Microchannel Luminescence Detectability Evaluation The protective film was peeled off from the photosensitive resin laminate obtained in the above <Preparation of photosensitive resin laminate 3>. By injection molding, an acrylic resin microchannel was produced, in which one side of the channel had a width of 70 μm, a depth of 30 μm, and a length of 2.5 mm and was connected to a circular through hole with a diameter of 5 mm. One set of nine channels, and 15 sets, were arranged radially on a circular substrate. Using a vacuum laminator manufactured by Takatori Co., Ltd., the photosensitive resin laminate shown in Table 1 was attached to the microchannel at a vacuum degree of 50 Pa and 70°C. After pasting, the sticker was exposed to 500 mJ/ ^cm2 using an exposure machine HMW-201KB manufactured by Oak Seisakusho Co., Ltd. to complete the sealing. A luminescence experiment was conducted using the luminescent substrate SuperSignal ^TM West Femto in the flow channel. The microchannel luminescence detectability was ranked as follows.
◎: Light emission can be detected without any problem.
○: The contrast of the emitted light is affected and the detection sensitivity is lowered.
△: The contrast of light emission is greatly affected and the detection sensitivity is lowered.
×: Luminescence cannot be detected.

5. Microchannel Water Resistance Evaluation The microchannel was sealed in the same manner as in "4. Microchannel Luminescence Detectability Evaluation" above to produce a microchannel. Ion-exchanged water was introduced into the microchannel, and 1 hour later, the state of the cured product of the photosensitive resin composition layer was observed. Water resistance was ranked as follows.
◎: No wrinkles observed.
○: Wrinkles are observed around the circular through hole.
△: Wrinkles are seen in a part of the flow path.
×: Wrinkles are seen throughout the channel.

6. Preparation of microchannel pattern <Preparation of microchannel pattern 1>
The protective film was peeled off from the photosensitive resin laminate obtained in <Preparation 1 of photosensitive resin laminate> above, and was placed on a 6-inch silicon wafer using an ordinary pressure laminator (VA-400III manufactured by Taisei Laminator Co., Ltd.). Lamination was carried out twice at a speed of 0.2 m/min, a cylinder pressure of 0.2 MPa, and a roll temperature of 70° C., and a 480 μm thick photosensitive resin composition layer and a support film were laminated on a 6-inch silicon wafer.

Next, using Nuvogo fine 10 manufactured by Nippon Orbotech Co., Ltd., the photosensitive resin composition layer was exposed to light at 1 J/cm ² and an ih light beam ratio of 0 to 100% to expose the channel pattern, and then the support After the film was peeled off, it was developed using a conveyor-type spray developing machine at 30° C. using a 1% by mass sodium carbonate aqueous solution for 1.5 times the minimum development time, washed with water and dried to obtain a channel pattern. FIG. 1 is a diagram showing a flow path pattern formed in an example, in which the area inside the frame of the pattern is an unexposed area, and the area outside the frame is an exposed area. The flow path pattern 1 is arranged in an arc shape such that the injection port 11 is located in the center direction of the silicon wafer, the waste liquid part 12 is located in the circumferential direction, and the weighing part 13 is located between the injection port 11 and the waste liquid part 12. A plurality of them are arranged within a silicon wafer. The weighing section 13 is composed of a plurality of microchannels for weighing, each having a long side (a), a short side (b), a width (c), and a partition width (d) as shown in FIG. has been done.

<Preparation of microchannel pattern 2>
Furthermore, a photosensitive resin laminate was produced in accordance with <Preparation of photosensitive resin laminate 1> using the formulation and film thickness as shown in Examples 7 to 12 in Table 3, and the above <Microchannel pattern Production 1>, the channel depth as shown in Examples 7 to 12 in Table 3, the channel long side (a), the channel short side (b), and the channel width (c) were prepared. A trapezoidal microchannel for weighing was fabricated. However, a circular acrylic plate was used as the base material. When the thickness of the photosensitive resin layer of the photosensitive resin laminate was small, an acrylic plate with a large diameter was required to arrange 96 channels. Moreover, when the development time per 25 μm is long, long-time development is required and productivity tends to be low.

Next, 10 μL of pure water was injected from the injection port, and by rotating with a spin coater, the pure water was dispensed from the injection port to a measuring section arranged circumferentially. When the film thickness exceeds 100 μm, the development time is 15 to 50 seconds/25 μm, and the photosensitive resin layer has the composition as in Example 1, liquid feeding control is good, the substrate area is small, A highly productive microchannel substrate can be obtained.

7. Mandrel evaluation <Preparation of photosensitive resin laminate 2>
The protective film was peeled off and removed from the photosensitive resin laminates produced with the photosensitive resin composition compositions of Examples 2 to 5, and a copper-clad laminate for flexible printed wiring boards manufactured by Nikkan Kogyo Co., Ltd., NIKAFLEX F-30VC1 25RC11(H ), exposed to 500 mJ/cm ² using an exposure machine HMW-201KB manufactured by Oak Seisakusho Co., Ltd., and developed for twice the minimum development time to produce a test piece with a width of 42 mm and a length of 20 cm. This was conditioned for one day at 23° C. and 50% relative humidity, and subjected to a bending test using a cylindrical mandrel tester, and the minimum value of the mandrel without cracking was taken as the mandrel evaluation value. Ranked as follows. The better this value is, the more flexible the microchannel can be produced.
◎: 3mmφ or less ○: More than 3mmφ and 6mmφ or less Δ: More than 6mmφ and 10mmφ or less ×: More than 10mmφ.

8. Support film adhesion strength evaluation <Preparation of photosensitive resin laminate 3>
The protective film was peeled off and removed from the photosensitive resin laminates 20 cm x 20 cm produced with the photosensitive resin composition compositions of Examples 1 to 6 and Comparative Examples 1 and 2, and a 20 cm x 20 cm copper-clad laminate was prepared with jet scrubbing. The film was laminated so that 20 cm x 10 cm of film remained on 10 cm. Thereafter, the photosensitive resin laminate was cut into a strip with a width of 1 inch using a cutter so as to straddle the portion laminated to the copper-clad laminate and the remaining portion of the film. In this way, a strip-shaped sample with a width of 1 inch was obtained, only half of which was laminated onto the copper-clad laminate. After that, the humidity was conditioned in an environment of 23°C and 50% relative humidity for one day, and the unlaminated part of the strip sample was held and subjected to a tensile test to evaluate the adhesion strength between the support film and the photosensitive resin composition layer. did. In the tensile test, the tensile test device was Tensilon RTM-500 manufactured by A&D Co., Ltd., and the peel angle was 180 degrees and the tensile speed was 100 m/min. The maximum value of adhesion strength was taken as the value of adhesion strength.

9. Support Film Adhesion Evaluation In "8. Support Film Adhesion Strength Evaluation", it was observed whether unnecessary peeling occurred between the support film and the photosensitive resin composition layer while preparing the tensile test sample. In addition, the surface of the photosensitive resin composition layer after the tensile test was observed to see if there were any peel lines. The observation results were ranked as follows.
◎: Neither unnecessary peeling nor peeling lines can be observed.
○: Either unnecessary peeling or peeling lines were observed.
×: Unnecessary peeling was observed in more than half of the area of the sample. Alternatively, peeling lines with obvious unevenness were observed.

1 Channel pattern 11 Inlet 12 Waste liquid section 13 Weighing section (a) Long side of the channel (b) Short side of the channel (c) Channel width (d) Partition width

Claims (7)

A photosensitive resin laminate for a microchannel device comprising a support film and a photosensitive resin composition layer,
The photosensitive resin laminate for a microchannel device has a transmittance of 80% or more at one or both wavelengths of 515 nm and 600 nm after exposure,
The adhesion strength between the support film and the photosensitive resin composition layer is 3 gf/inch or more and 100 gf/inch or less,
Photosensitive resin laminate for microchannels. The photosensitive resin laminate for microchannels according to claim 1, which is for direct exposure. The photosensitive resin composition layer is composed of a photosensitive resin composition having a ratio (I/O) of inorganic value (I) to organic value (O) of 1.0 or less. 3. The photosensitive resin laminate for microchannels according to 1 or 2. The photosensitive resin laminate for microchannels according to any one of claims 1 to 3, wherein the photosensitive resin composition layer has an elastic modulus of 2 GPa or less and a breaking elongation of 30% or more after exposure. The photosensitive resin laminate for a microchannel according to any one of claims 1 to 4, wherein the photosensitive resin composition layer has a thickness of 100 μm or more. Any one of claims 1 to 5, wherein the thickness of the photosensitive resin composition layer is such that the development time per 25 μm using a 1% by mass Na ₂ CO ₃ aqueous solution at 30° C. is 15 to 50 seconds/25 μm. The photosensitive resin laminate for microchannels described in . The photosensitive resin composition layer includes (a) an alkali-soluble polymer having a carboxyl group, (b) an addition polymerizable monomer, and (c) a photopolymerization initiator,
(b) The addition polymerizable monomer is the following (Formula I):
C-((CH ₂ )R ¹ )((CH ₂ )R ² )((CH ₂ )R ³ )((CH ₂ )R ⁴ )
...(Formula I)
(In the formula, R ¹ to R ⁴ each independently represent a monovalent organic group.)
According to any one of claims 1 to 6, the composition comprises a monomer having a structure represented by and having a molecular weight of 200 to 600 in an amount of 50% by mass or more in (b) addition polymerizable monomer. Photosensitive resin laminate for microchannels.

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