JP4760463B2 - Photosensitive resin composition, photosensitive film, method for producing microchemical chip using these, and microchemical chip - Google Patents

Description

  The present invention relates to a photosensitive resin composition, a photosensitive film, a microchemical chip manufacturing method using these, and a microchemical chip.

  In recent years, research on microchemical chips that downsize and integrate chemical experiments and chemical operations has attracted rapid attention. In chemical experiments using microchemical chips, various advantages such as reduction of reagent amount and waste liquid amount, space saving and portability are brought about. In addition, since this chemical process can be integrated and miniaturized in the same manner as a semiconductor integrated circuit, measurement time can be greatly shortened and efficiency can be increased.

  In order to perform various chemical processes on a chip of several centimeters, a micro chemical chip has a fine channel of several tens to several hundreds of μm formed on a glass substrate, and moves and mixes in the channel. , Reaction, separation, detection and the like can be performed. A chemical system / analysis system using such a microchemical chip is called a micro chemical analysis system (μ-TAS: micro total analysis system).

  As a chip for performing a chemical process on a microchemical chip, a microreactor chip or a chip for combinatorial synthesis can be given as representative examples. Examples of the analytical device include an electrophoresis chip and a liquid chromatography chip for the purpose of separating and analyzing genes, proteins, cell components, and the like. On these microchemical chips, there are formed channels for moving, mixing, reacting, separating, detecting, and the like.

  Conventionally, methods for producing a flow path to a substrate for a microchemical chip include a method of transferring a mold to a plastic substrate and injection molding. However, in these methods, it is necessary to produce a mold. Since it takes enormous cost and time to produce this mold, there is a problem that it is not possible to flexibly cope with a design change.

  In addition, a method of forming a flow path in a glass substrate generally uses wet etching using hydrofluoric acid as an etchant, but it is necessary to form chromium and gold on the glass substrate as a mask and further form a resist. There is a problem that the number is increased and the cost is high because the material is expensive.

  In general, methods such as friction bonding, heat melting bonding, solder bonding, and anodic bonding are used to bond a glass substrate, a Si substrate, or the like serving as a lid to a glass substrate on which a flow path is formed. Each of these methods has a problem that it is a large process at a high temperature.

In order to solve the above problem, a flow path forming method using a photosensitive resin composition has been studied (for example, see Patent Document 1). However, in this method, since an insulating layer such as SiO ₂ is provided on the photosensitive resin composition layer, when the substrate serving as the lid is a glass substrate, the above-described large-scale bonding process is required. Arise.

JP 2004-170293 A

An object of the present invention is to solve at least one of the above-described problems, and a microchemical chip having a fine pattern can be easily adapted to various channel designs. Furthermore, it is to provide a photosensitive resin composition and a photosensitive film that can be prepared without requiring a large joining step depending on the configuration of the microchemical chip.
Another object of the present invention is to solve at least one of the above-described problems. A microchemical chip having a fine pattern can be easily and variously designed for various channels. In addition, the present invention provides a method for manufacturing a microchemical chip that can provide a substrate serving as a lid without requiring a large joining step depending on the configuration of the microchemical chip.
Another object of the present invention is to solve at least one of the above-mentioned problems, and has a fine pattern and can easily cope with various flow path designs. It is possible to provide a microchemical chip that can be manufactured by a simple process with low manufacturing cost.

The present invention is as follows.
The present invention is a photosensitive resin composition for forming a flow path of a microchemical chip, wherein the photosensitive resin composition comprises (A) a binder polymer, (B) a photopolymerizable compound, and (C). The present invention relates to a photosensitive resin composition comprising a photopolymerization initiator, wherein the photopolymerizable compound (B) contains a photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule.
It is preferable that the photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule further has at least one hydroxyl group in the molecule.
Moreover, this invention relates to the photosensitive film provided with a support body and the photosensitive resin composition layer which consists of the said photosensitive resin composition formed on the said support body.
The present invention also includes a step of laminating a photosensitive resin composition layer on the substrate using the photosensitive resin composition or the photosensitive film, and an actinic ray at a predetermined portion of the photosensitive resin composition layer. The present invention relates to a method for producing a microchemical chip comprising a step of irradiating and photocuring an exposed portion, and a step of forming a photocured product pattern by removing an unexposed portion.
The manufacturing method preferably further includes a step of bonding an insulating base material having a through hole on the photocured material pattern.
The present invention also includes a step of laminating a photosensitive resin composition layer on the substrate using the photosensitive resin composition or the photosensitive film, and an actinic ray at a predetermined portion of the photosensitive resin composition layer. Including a step of irradiating and photocuring an exposed portion, a step of removing an unexposed portion to form a photocured material pattern, and a step of forming a groove in the substrate by etching the substrate using the photocured material pattern as a mask. The present invention relates to a method for producing a microchemical chip.
The manufacturing method preferably further includes a step of peeling the photocured product pattern and a step of bonding an insulating base material having a through hole to the surface of the substrate provided with the groove.
Further, the present invention is a microchemical chip including a substrate, a flow path pattern laminated on the substrate, and an insulating base material laminated on the flow path pattern, wherein the flow path pattern cures the photosensitive resin composition. The present invention relates to a microchemical chip characterized in that a substrate and a flow path pattern are bonded to each other, and the flow path pattern and an insulating substrate are bonded to each other.
The present invention also relates to a microchemical chip including a substrate having a groove serving as a flow path, and an insulating base material laminated on a surface having the groove of the substrate, wherein the groove forms a substrate using the flow path pattern as a mask. Formed by etching, the flow path pattern is a pattern formed by curing the photosensitive resin composition, and the photosensitive resin composition comprises a support and a photosensitive resin composition formed on the support The present invention relates to a microchemical chip provided on a substrate using a photosensitive film comprising a photosensitive resin composition layer made of a product.
The photosensitive resin composition used for forming the microchemical chip of the present invention is preferably the above-described photosensitive resin composition.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition excellent in the adhesiveness on a microchemical chip board | substrate, a photosensitive film, and the manufacturing method of a microchemical chip using these can be provided. According to the photosensitive resin composition, photosensitive film, and microchemical chip manufacturing method using the same of the present invention, a microchemical chip having a fine pattern can be easily and easily applied to various channel designs. Furthermore, depending on the configuration of the microchemical chip, a substrate serving as a lid can be provided without requiring a large joining step.
In addition, the microchemical chip of the present invention can have a fine pattern and can easily cope with various channel designs.

Hereinafter, the present invention will be described in detail.
The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound, and (C) a photopolymerization initiator.

  Examples of the (A) binder polymer in the present invention include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, and phenol resins. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more binder polymers. Examples of combinations of two or more types of binder polymers include two or more types of binder polymers composed of different copolymer components, two or more types of binder polymers having different weight average molecular weights, and two or more types of binder polymers having different degrees of dispersion. It is done. A polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used. In addition, the binder polymer may have a photosensitive group as necessary.

  The binder polymer of component (A) can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyl toluene, α-methyl styrene, p-methyl styrene, and p-ethyl styrene, and vinyl alcohols such as acrylamide, acrylonitrile, and vinyl n-butyl ether. Esters of (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2 , 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) Acrylic acid, β-furyl (meth) Maleic acid monoesters such as crylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic Acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These may be used alone to form a homopolymer, or two or more types may be combined to form a copolymer.

  Here, (meth) acrylic acid in the present invention means acrylic acid and methacrylic acid corresponding thereto, and (meth) acrylate means acrylate and methacrylate corresponding thereto.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more. (A) The binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the binder polymer is obtained by radical polymerization of a polymerizable monomer having a carboxyl group and other polymerizable monomers. Can be manufactured. The polymerizable monomer having a carboxyl group is preferably methacrylic acid from the viewpoint of stability. (A) The acid value of the binder polymer is preferably 30 mgKOH / g or more from the viewpoint of development time, and is preferably 250 mgKOH / g or less from the viewpoint of developer resistance of the photocured resist, preferably 45 to 200 mgKOH. / G is more preferable. When performing development with a solvent as the development step, it is preferable to prepare while suppressing the amount of polymerizable monomer having a carboxyl group. (A) The weight average molecular weight of the binder polymer (measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene) is preferably 20,000 or more from the viewpoint of developer resistance. From the viewpoint of shortening the development time, it is preferably 300,000 or less, more preferably 25,000 to 150,000, and particularly preferably 30,000 to 100,000.

  The photopolymerizable compound of component (B) in the present invention includes a photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule. The photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule may further have at least one hydroxyl group in the molecule. The photopolymerizable compound of component (B) includes a photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule, at least one hydroxyl group, at least one unsaturated group and isocyanuric in the molecule. Both photopolymerizable compounds having a ring structure can also be included.

  As a photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule, for example, a compound represented by the general formula (I) is preferable from the viewpoint of adhesion.

〔式中、Ｒ^１は、各々独立に、

（式中、Ｒ^２は、水素原子又はメチル基を示し、ｍは１〜１４の整数である）、

（式中、ｍは１〜１４の整数である）、又は、

（式中、Ｒ^２は水素原子又はメチル基を示し、ｎは１〜９の整数であり、ｍは１〜１４の整数である）を示す。但し、Ｒ^１の少なくとも１つは、一般式（ＩＩ）又は一般式（ＩＶ）である。〕で表される化合物を用いることが好ましい。

[Wherein R ^{1 s} are each independently

(Wherein R ² represents a hydrogen atom or a methyl group, m is an integer of 1 to 14),

(Wherein m is an integer from 1 to 14), or

(Wherein R ² represents a hydrogen atom or a methyl group, n is an integer of 1 to 9, and m is an integer of 1 to 14). However, at least one of R ¹ is general formula (II) or general formula (IV). It is preferable to use a compound represented by

Photopolymerizable compound is at least one hydroxyl group in the molecule, if it has at least one unsaturated group and an isocyanuric ring structure, at least one of R ¹ is a formula (III), and, at least one of R ¹ One is general formula (II) or general formula (IV).

  In general formula (II) or general formula (III), m is an integer of 1-14, and it is preferable that it is 1-6. When m exceeds 14, chemical resistance may deteriorate. Moreover, in general formula (IV), m is an integer of 1-14, it is preferable that it is 1-6, n is an integer of 1-9, and it is preferable that it is 3-6. When m exceeds 14, chemical resistance may be reduced, and when n exceeds 9, mechanical strength may be reduced.

The photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule is particularly preferably a compound represented by the general formula (V).

As the photopolymerizable compound having at least one hydroxyl group, at least one unsaturated group and an isocyanuric ring structure in the molecule, a compound represented by the general formula (VI) is particularly preferable.

Examples of commercially available compounds represented by the above general formula (I) include, for example, NK Oligo UA-21 (trade name of Shin-Nakamura Chemical Co., Ltd., general formula (I), wherein R ¹ is all represented by the general formula (III)), M-315 (trade name of Toa Gosei Co., Ltd., general formula (I), wherein R ¹ is all the general formula (II)), M-215 (trade name of Toa Gosei Co., Ltd.) In general formula (I), two R ¹ are general formula (II), and one R ¹ is general formula (III).

  The content of the photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule should be 1 to 40 parts by weight with respect to 100 parts by weight of the total amount of the component (A) and the component (B). Is preferable, it is more preferable to set it as 3-30 weight part, and it is still more preferable to set it as 6-25 weight part. If this content is less than 1 part by weight, the adhesion to glass tends to be inferior, and if it exceeds 40 parts by weight, the fluidity increases and the photosensitive resin composition is formed from the end when the photosensitive film is wound up. There is a tendency for problems such as bleeding (edge fusion) to occur.

  Further, as the component (B) other than the photopolymerizable compound having at least one unsaturated group and isocyanuric ring structure in the molecule, a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule is preferably used. It is done. Examples thereof include bisphenol A-based (meth) acrylate compounds. Although there is no restriction | limiting in particular in a bisphenol A type (meth) acrylate compound, For example, it is preferable that it is a compound represented by general formula (VII).

In the general formula (VII), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. In the general formula (VII), X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. In the general formula (VII), p and q are positive integers selected such that p + q = 4 to 40, preferably 6 to 34, more preferably 8 to 30, and more preferably 8 to 28 is particularly preferred, 8-20 is very preferred, 8-16 is very particularly preferred, and 8-12 is very particularly preferred. When p + q is less than 4, the compatibility with the component (A) tends to decrease, and when p + q exceeds 40, the hydrophilicity increases and the water absorption rate of the photocured product pattern tends to increase. Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group.

  In addition, the aromatic ring in the general formula (VII) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cyclohexane having 3 to 10 carbon atoms. Alkyl group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, A C1-C10 alkyl mercapto group, an allyl group, a hydroxyl group, a C1-C20 hydroxyalkyl group, a carboxyl group, a C1-C10 carboxyalkyl group, and a C1-C10 alkyl group. 10 acyl groups, C1-C20 alkoxy groups, C1-C20 alkoxycarbonyl groups, C2-C10 alkylcarbonyl groups, C2-C10 Alkenyl group, N- alkylcarbamoyl group or a group containing a heterocyclic ring having 2 to 10 carbon atoms, an aryl group substituted by these substituents. The above substituents may form a condensed ring. Moreover, the hydrogen atom in these substituents may be substituted with the above substituents such as a halogen atom. When the number of substituents is 2 or more, each of the two or more substituents may be the same or different.

  Examples of the compound represented by the general formula (VII) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic). Loxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) Examples thereof include bisphenol A-based (meth) acrylate compounds such as propane.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is BPE- 00 (made by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available, and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is BPE-1300 (Shin-Nakamura Chemical Industry) It is commercially available as a product name). These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) a) Liloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl) propane, 2,2-bis (4-((meta And acryloxyhexadecapropoxy) phenyl) propane. These may be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These may be used alone or in combination of two or more.

  Examples of the compound similar to the bisphenol A-based (meth) acrylate compound include a compound obtained by adding acrylic acid to bisphenol A-diepoxy. Viscoat # 540 (product name, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is commercially available. These may be used alone or in combination of two or more.

  Examples of the photopolymerizable compound (B) other than the bisphenol A (meth) acrylate compound include tricyclodecane dimethanol, neopentyl glycol-modified trimethylolpropane diacrylate, and, for example, α, β-unsaturated polyhydric alcohol. Compounds obtained by reacting carboxylic acids, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene ( (Meth) acrylate, [gamma] -chloro- [beta] -hydroxypropyl- [beta]-(meth) acryloyloxyethyl-o-phthalate, [beta] -hydroxyethyl- [beta]-(meth) acryloyloxyethyl-o-phthalate, [beta] -hydroxypropyl -Β '-(meth) acryloyloxy Examples include ethyl-o-phthalate, (meth) acrylic acid alkyl ester, and EO-modified nonylphenyl (meth) acrylate. These may be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. It is done.

  As the photopolymerization initiator of the component (C) in the present invention, an optionally substituted hexaarylbiimidazole is preferably used. For example, 2- (o-chlorophenyl) -4,5-diphenylimidazole 2-mer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxy) Phenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like. Further, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. From the viewpoint of adhesion and sensitivity, a 2,4,5-triarylimidazole dimer which may have a substituent is more preferable. Further, as the component (C) other than the hexaarylbiimidazole which may have a substituent, benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′— Tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [ Aromatic ketones such as 4- (methylthio) phenyl] -2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3 -Benzanthraquinone, 2-phenylanthraquinone, 2, -Quinones such as diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin Benzoin ether compounds such as methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyldimethyl ketal, 9-phenylacridine, 1,7-bis (9,9 Examples include acridine derivatives such as' -acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, and coumarin compounds. Moreover, a combination of a thioxanthone compound and a tertiary amine compound may be used, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. These are used alone or in combination of two or more.

  The content of component (A) is preferably in the range of 40 to 80 parts by weight, more preferably 45 to 70 parts by weight, with respect to 100 parts by weight of the total amount of components (A) and (B). preferable. If this content is less than 40 parts by weight, the photocured product tends to be brittle and tends to be inferior in coating properties. If it exceeds 80 parts by weight, the sensitivity tends to be insufficient. The content of the component (B) is preferably in the range of 20 to 60 parts by weight, more preferably 30 to 50 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B). preferable. If this content is less than 20 parts by weight, the resolution tends to decrease, and if it exceeds 60 parts by weight, edge fusion tends to occur.

  Moreover, when it contains a photopolymerizable compound other than the photopolymerizable compound having at least one unsaturated group and an isocyanuric ring structure in the molecule, the content is 100 weights of the total amount of the component (A) and the component (B). It is preferable to set it as the range of 1-40 weight part with respect to a part, It is more preferable to set it as 5-35 weight part, It is especially preferable to set it as 10-30 weight part. If this content is less than 1 part by weight, the resolution tends to decrease, and if it exceeds 40 parts by weight, it tends to be difficult to form a film.

  The content of the (C) photopolymerization initiator is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the components (A) and (B), and 0.2 to 10 parts by weight. More preferably, it is a part. If this content is less than 0.1 part by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be. As content of hexaarylbiimidazole in (C) component, it is preferable that it is 10 to 90 weight%, and it is more preferable that it is 20 to 80 weight%. If the content is less than 10% by weight, the adhesion tends to be insufficient, and if it exceeds 90% by weight, the development sludge tends to increase during the development processing.

  The resin composition containing the components as described above may further include a dye such as malachite green, a photochromic agent such as tribromophenyl sulfone or leuco crystal violet, a thermochromic inhibitor, p-toluenesulfonamide or the like, if necessary. Plasticizers, pigments, fillers, antifoaming agents, flame retardants, stabilizers, adhesion-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. (B) About 0.01-20 weight part of each can be contained with respect to 100 weight part of total amounts of a component. These may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention containing the components as described above can be obtained, for example, by uniformly kneading and mixing the contained components with a roll mill, a bead mill or the like. If necessary, it can be dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof to obtain a solid content of 30 It can be used as a solution of about ˜60% by weight.

  A method for forming a photosensitive material composition layer on a microchemical chip substrate using the obtained photosensitive resin composition is not particularly limited, but the photosensitive resin composition is applied as a liquid resist on the substrate. And can be dried. Moreover, a protective film can be coat | covered on the photosensitive resin composition layer as needed. Further, as will be described in detail later, it is preferable to use the photosensitive resin composition layer in the form of a photosensitive film. The thickness of the photosensitive resin composition layer to be applied varies depending on the use, but is preferably about 1 to 100 μm after drying. Examples of the protective film in the case where the protective film is used after being coated as a liquid resist include polymer films such as polyethylene and polypropylene.

  Next, the photosensitive film which concerns on this invention, ie, the photosensitive film formed by forming the resin composition layer which consists of the resin composition of this invention mentioned above on a support body, is demonstrated.

  The photosensitive film includes a support and a photosensitive resin composition layer formed thereon. As the support, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester can be preferably used. The thickness of the polymer film is preferably about 1 to 100 μm. Although the formation method of the photosensitive resin composition layer on a support body is not specifically limited, It can implement preferably by apply | coating and drying the solution of the photosensitive resin composition. The thickness of the photosensitive resin composition layer to be applied varies depending on the use, but is preferably about 1 to 100 μm after drying. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Drying can be performed at 70 to 150 ° C. for about 5 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step. You may coat | cover the photosensitive resin composition layer surface using the said polymer film used as a support body as a protective film. As the protective film, those having a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support are preferable, and a film having a low fish eye is preferable. Furthermore, the photosensitive film may have an intermediate layer and a protective layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer in addition to the photosensitive resin composition layer, the support, and any protective film. Good.

  The produced photosensitive film is usually wound around a cylindrical core and stored. In addition, it is preferable to wind up so that a support body may become an outer side at this time. An end face separator is preferably installed on the end face of the roll-shaped photosensitive film roll from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

  Next, the manufacturing method of the microchemical chip of this invention is demonstrated. A method for producing a microchemical chip includes a step of laminating a photosensitive resin composition layer on a substrate using a photosensitive resin composition or a photosensitive film, and an active ray on a predetermined portion of the photosensitive resin composition layer. It includes a step of irradiating and photocuring the exposed portion and a step of removing the unexposed portion and forming a photocured product pattern. Furthermore, you may have an arbitrary process. As an optional step, it is preferable to include a step of bonding an insulating base material having a through hole on the photocured material pattern. Thereby, the microchemical chip which uses a removal part as a flow path is obtained.

First, the above-described photosensitive resin composition layer of the present invention is laminated on a substrate for a microchemical chip. Examples of the substrate include an insulating substrate such as a glass substrate or a polymer substrate, a semiconductor substrate such as a silicon substrate, or a semiconductor substrate on which an electrode such as ITO is formed. As the laminating method, the coating method described above can be used, and a photosensitive film can also be used. When the protective film is present on the photosensitive resin composition layer, the lamination method using the photosensitive film is laminated on the substrate while removing the protective film. As the lamination condition, for example, by heating the photosensitive resin composition layer to about 70 to 130 ° C., pressure bonding is performed on the substrate at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ). The method of laminating | stacking etc. is mentioned, It is also possible to laminate | stack under reduced pressure. The shape of the substrate surface is usually flat, but may be uneven or an electrode pattern may be formed.

  After laminating the photosensitive resin composition, the photosensitive resin layer in the exposed area is photocured by irradiating an actinic ray in an image form. As a method of irradiating an actinic ray in an image form, there is a method of irradiating an actinic ray in an image form on a photosensitive resin layer through a mask pattern and photocuring the photosensitive resin layer in an exposed portion. The mask pattern may be a negative type or a positive type, and a commonly used one can be used. As the light source of actinic light, a known light source, for example, a light source that effectively emits ultraviolet light, visible light, or the like, such as a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp is used. Further, laser direct drawing exposure can be performed without using a mask pattern.

  As shown in FIG. 1, after the exposure, the photosensitive resin composition layer in the unexposed portion is selectively removed by development, whereby the photocured product pattern 2 (removal portion 5 is formed on the substrate 3 for the microchemical chip. A pattern made of a photocured product as a flow path) is formed. In the development step, when a support is present, the support is removed prior to development. Development is performed by removing unexposed portions by wet development, dry development, or the like using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. In the present invention, it is preferable to use an alkaline aqueous solution. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like. . The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

  As a process after the development, the formed photocured product pattern may be further cured by a heat treatment at about 60 to 250 ° C. as necessary.

As shown in FIG. 3, by forming a cover of the insulating base material 1 or the like (FIG. 2) provided with a through hole 4 on the photocured product pattern after forming the photocured product pattern, for example, the microchemical chip 6 can be simplified. Can be made. As a method of covering with the insulating base material 1 or the like provided with the through-holes 4, for example, the photocured material pattern is penetrated while being heated to about 70 to 150 ° C. by using the fine adhesion on the photocured material pattern. Examples thereof include a method of laminating the insulating base material 1 and the like provided with the holes 4 by press-bonding the insulating base material 1 and the like to the photocured material pattern with a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ). It is also possible to laminate under reduced pressure. Further, after the insulating base material 1 provided with the through holes 4 is laminated, a heat treatment at about 60 to 250 ° C. is performed in order to completely bond the photocured material pattern and the insulating base material 1 provided with the through holes 4. Is preferred. As the insulating substrate, for example, a glass substrate or a polymer substrate can be used.

  FIG. 4 shows a cross-sectional view of the microchemical chip 6 obtained by the above method. In the figure, reference numeral 5 denotes a photosensitive resin composition removing portion (unexposed portion). In the microchemical chip 6, the removing portion 5 serves as a flow path.

  In addition, another manufacturing method of the microchemical chip will be described. This method includes a step of laminating a photosensitive resin composition layer on a substrate using a photosensitive resin composition or a photosensitive film, and exposing a predetermined portion of the photosensitive resin composition layer with active light. A step of photocuring a portion, a step of removing a non-exposed portion to form a photocured product pattern, and a step of forming a groove in the substrate by etching the substrate using the photocured product pattern as a mask. Furthermore, you may have an arbitrary process. As an optional step, it is preferable to include a step of peeling the photocured product pattern and a step of bonding an insulating base material having a through hole to the surface of the substrate provided with a groove. As a result, a microchemical chip using the etched portion (groove) of the substrate as a flow path is obtained.

  The step of laminating the photosensitive resin composition layer, the step of photocuring the exposed portion, and the step of forming the photocured product pattern can be performed in the same manner as the above-described production method. For example, as shown in FIG. 6, when the microchemical chip substrate is a glass substrate 13, the glass substrate 13 is wet-etched using the heat-treated photocured material pattern (resist pattern) 12 as a mask to form a flow path. A groove 17 is formed. Thereafter, as shown in FIG. 7, it is preferable to peel the resist pattern and bond a glass substrate or the like (FIG. 2) provided with a through hole to the surface of the flow path forming portion by friction bonding or heat melting bonding. As an etchant used for wet etching, hydrofluoric acid, hydrofluoric acid and other acids such as acetic acid, hydrochloric acid, sulfuric acid, formic acid or the like can be used, but there is no particular limitation as long as etching is possible.

  FIG. 5 shows a cross-sectional view of the microchemical chip 16 obtained by the above method. In the figure, 17 is a groove provided in the glass substrate, and the groove 17 becomes a flow path.

  Furthermore, the macrochemical chip of the present invention will be described. The microchemical chip of the present invention is a microchemical chip including a substrate, a flow path pattern laminated on the substrate, and an insulating base material laminated on the flow path pattern, wherein the flow path pattern is a photosensitive resin composition. Is a pattern formed by curing, and is characterized in that the substrate and the flow path pattern are bonded, and the flow path pattern and the insulating base material are bonded. As the photosensitive resin composition, either a negative photosensitive resin composition or a positive photosensitive composition can be used. Such a microchemical chip can be produced by using the above-described photosensitive resin composition or photosensitive film and by the above-described microchemical chip manufacturing method.

  In the microchemical chip of the present invention, the substrate and the insulating base material are bonded together by a flow path pattern formed using the photosensitive resin composition. An example of such a microchemical chip is the microchemical chip shown in FIG.

  The microchemical chip of the present invention is a microchemical chip including a substrate having a groove serving as a flow path, and an insulating base material laminated on a surface having the groove of the substrate, wherein the groove has a flow path pattern. Formed by etching the substrate as a mask, the flow path pattern is a pattern formed by curing the photosensitive resin composition, and the photosensitive resin composition was formed on the support and the support It was provided on the board | substrate using the photosensitive film provided with the photosensitive resin composition layer which consists of photosensitive resin compositions. As the photosensitive resin composition, either a negative photosensitive resin composition or a positive photosensitive composition can be used. Such a microchemical chip can be produced by using the above-described photosensitive film and the above-described microchemical chip manufacturing method.

  In the microchemical chip of the present invention, the substrate and the insulating base material are bonded together by anodic bonding, friction bonding, hot melt bonding (600 ° C. or higher), and the like. An example of such a microchemical chip is the microchemical chip shown in FIG.

  As a conventional method for producing a flow path to a substrate for a microchemical chip, when a plastic substrate is used, there are a method of transferring a mold, injection molding, and the like. However, these methods need to produce a mold. Since it takes enormous cost and time to produce this mold, there is a problem that it is not possible to flexibly cope with a design change. In addition, when a glass substrate is used, hydrofluoric acid is generally used as an etchant for wet etching of the glass substrate. However, since chromium and gold and a resist are formed on the glass substrate as a mask, the number of processes increases and the material is expensive. Therefore, there is a problem of high cost.

  The photosensitive resin composition of the present invention can be laminated on a microchemical chip substrate, a predetermined pattern can be formed by exposure and development, and the resulting pattern itself can be used as a flow path. Alternatively, the channel can be formed in the substrate by etching the underlying microchemical chip substrate by wet etching using the predetermined pattern as a mask. If the photosensitive resin composition of the present invention is used, since there is no need for a mold, it is possible to provide microchemical chips of various designs having a fine flow path pattern easily at low cost. In addition, since it is not necessary to form a chromium and gold layer, the number of steps can be reduced and the cost can be reduced.

  Furthermore, a lid base material can be bonded onto the pattern by utilizing the slight adhesion of the pattern formed using the photosensitive resin composition. Usually, in a microchemical chip, when packaging using a cover glass or the like, it becomes a large process at a high temperature such as anodic bonding, friction bonding, and thermal fusion bonding, but depending on the configuration of the microchemical chip, As long as a photocured product pattern is prepared using a photosensitive resin composition, a cover glass or the like can be joined simply by heat-treating by applying pressure or pressure under normal pressure or vacuum using the light adhesion of the photocured product pattern. it can.

  Further, the microchemical chip of the present invention has a flow path pattern formed by curing the photosensitive resin composition between the substrate and the base material serving as a lid. Since the flow path pattern formed by curing the photosensitive resin composition is excellent in adhesion, resolution, etc., it is possible to easily obtain micro chemical chips of various designs having a fine flow path pattern at low cost. In general, since a resin obtained by curing a photosensitive resin composition has a cross-linked structure, it has excellent chemical resistance, and the flow path swells or dissolves even when a sample is passed through the flow path. There are few things. In particular, a microchemical chip using a specific photosensitive resin composition can be preferably used when an acidic aqueous solution or an organic solvent is allowed to flow as a sample.

  Further, another microchemical chip of the present invention can be obtained by etching a substrate using a flow path pattern formed by curing a photosensitive resin composition as a resist pattern. Therefore, it is possible to easily produce microchemical chips having various designs having a fine flow path pattern at low cost without requiring a conventional mold.

  Although the field in which the microchemical chip is used is wide-ranging, the microchemical chip using the photosensitive resin composition of the present invention can be suitably used mainly in the biochemical field or the environmental field.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention. In the examples, “%” means% by weight.

(Experimental Examples 1 and 2, Reference Examples 3-6)
The materials shown in Table 1 were mixed with stirring to obtain a solution (photosensitive resin composition solution) forming a resin composition layer.
The binder polymer as component (A) in Table 1 was synthesized according to the following synthesis example.

(Synthesis example)
[Synthesis of binder polymer]
To a flask equipped with a stirrer, a reflux condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, 500 g of a mixture of methyl cellosolve and toluene having a weight ratio of 3: 2 is added, and stirred while blowing nitrogen gas. Heated to 85 ° C. On the other hand, 150 g of methacrylic acid as a polymerizable monomer, 110 g of methacrylic acid methyl ester, 65 g of acrylic acid ethyl ester, 50 g of butyl methacrylate, 125 g of styrene and 2.5 g of azobisisobutyronitrile (hereinafter referred to as “polymeric monomer”) The solution a was added dropwise to the above mixture of methyl cellosolve and toluene having a weight ratio of 3: 2 heated to 85 ° C. over 4 hours, and then stirred at 85 ° C. Incubated for 2 hours. Further, a solution prepared by dissolving 0.5 g of azobisisobutyronitrile in 150 g of a mixture of methyl cellosolve and toluene having a weight ratio of 3: 2 was dropped into the flask over 10 minutes. Mixing acetone and propylene glycol monomethyl ether in a weight ratio of 3: 2 so that the solution after dripping is kept at 85 ° C. for 5 hours with stirring and then cooled to have a non-volatile content (solid content) of 43% by weight. Dilution with a solvent gave a binder polymer. The obtained binder polymer had a weight average molecular weight of 50,000, a dispersity of 2.0, and an acid value of 195 mgKOH / g.
In addition, the weight average molecular weight of the binder polymer was measured by a gel permeation chromatography method and was derived by conversion using a standard polystyrene calibration curve. The measurement conditions of gel permeation chromatography (GPC) are shown below.
(GPC measurement conditions)
Pump: Hitachi L-6000 type (manufactured by Hitachi, Ltd.)
Column: Gelpack GL-R420 + Gelpack GL-R430 +
Gelpack GL-R440 (3 in total) (above, product name, manufactured by Hitachi Chemical Co., Ltd.)
Eluent: Tetrahydrofuran Measurement temperature: Room temperature Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

＊１；２−（２−クロロフェニル）−１−［２−（２−クロロフェニル）−４，５−ジフェニル−１，３−ジアゾール−２−イル］−４，５−ジフェニルイミダゾール、保土ヶ谷化学工業株式会社製 商品名：Ｂ−ＣＩＭ
＊２；Ｎ，Ｎ’−テトラエチル−４，４’−ジアミノベンゾフェノン、保土ヶ谷化学工業株式会社製 商品名：ＥＡＢ
＊３；ロイコクリスタルバイオレット、山田化学株式会社製 商品名：ＬＣＶ
＊４；ビス（アクリルオキシエチル）ヒドロキシエチルイソシアヌレート、東亜合成株式会社製 商品名：Ｍ−２１５
＊５；ペンタエリスリトールトリアクリレート、日本化薬株式会社社製 商品名：ＰＥＴ−３０
＊６；トリス（アクリロキシエチル）イソシアヌレート、東亜合成株式会社製 商品名：Ｍ−３１５
＊７；トリス（メタクリロイルオキシテトラエチレングリコールイソシアナートヘキサメチレン）イソシアヌレート、新中村化学工業株式会社製 商品名：ＵＡ−２１
＊８；γ−クロロ−２−ヒドロキシプロピル−β’−メタクリロイルオキシエチル−ｏ−フタレート、大阪有機化学工業株式会社製 商品名：ＦＡ−ＭＥＣＨ
＊９；ノニルフェニルＥＯ変性モノアクリレート、東亜合成株式会社製 商品名：Ｍ−１１３
＊１０；ＥＯ変性ビスフェノールＡジメタクリレート、日立化成工業株式会社製 商品名：ＦＡ−３２１Ｍ
＊１１；トリメチロールプロパンＥＯ変性トリアクリレート、日立化成工業株式会社製 商品名：ＴＭＰＴ−２１

* 1; 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole, Hodogaya Chemical Co., Ltd. Product name: B-CIM
* 2; N, N′-tetraethyl-4,4′-diaminobenzophenone, manufactured by Hodogaya Chemical Co., Ltd. Product name: EAB
* 3: Leuco Crystal Violet, manufactured by Yamada Chemical Co., Ltd. Product name: LCV
* 4; Bis (acryloxyethyl) hydroxyethyl isocyanurate, manufactured by Toa Gosei Co., Ltd. Product name: M-215
* 5: Pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd. Brand name: PET-30
* 6; Tris (acryloxyethyl) isocyanurate, manufactured by Toa Gosei Co., Ltd. Product name: M-315
* 7; Tris (methacryloyloxytetraethylene glycol isocyanate hexamethylene) isocyanurate, manufactured by Shin-Nakamura Chemical Co., Ltd. Product name: UA-21
* 8; γ-chloro-2-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate, manufactured by Osaka Organic Chemical Industry Co., Ltd. Product name: FA-MECH
* 9: Nonylphenyl EO-modified monoacrylate, manufactured by Toa Gosei Co., Ltd. Product name: M-113
* 10; EO-modified bisphenol A dimethacrylate, manufactured by Hitachi Chemical Co., Ltd. Trade name: FA-321M
* 11; Trimethylolpropane EO-modified triacrylate, manufactured by Hitachi Chemical Co., Ltd. Trade name: TMPT-21

  Next, the solution of the photosensitive resin composition obtained in Table 1 was uniformly applied onto a 16 μm-thick polyethylene terephthalate film, dried for 10 minutes with a hot air convection dryer at 100 ° C., and then a polyethylene protective film ( Tensile strength in the film longitudinal direction: 16 Mpa, tensile strength in the film width direction: 12 Mpa, trade name: NF-15, manufactured by Tamapoly Co., Ltd.) to obtain a photosensitive film. The film thickness after drying of the photosensitive resin composition layer was 40 μm.

On the other hand, a glass substrate (Pyrex glass (registered trademark); length 60 mm, width 50 mm, thickness 0.5 mm) was washed with isopropyl alcohol and air-dried. A glass substrate is heated to 80 ° C., and the photosensitive film is heated to 110 ° C. while peeling the polyethylene protective film so that the photosensitive resin composition layer is in contact with the glass surface. Laminated through a roll. The resulting laminate has a glass substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom.
The obtained laminate was evaluated for adhesion, resolution, and chemical resistance. The evaluation results are shown in Table 2.

<Evaluation of adhesion>
Using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM1201 having a high-pressure mercury lamp, the line width / space width was increased from 30/400 to 200/400 (unit: μm, line width increased to 5 μm) as a negative for resolution evaluation. A phototool having a wiring pattern with a constant space width) and a phototool having a 41-step tablet are brought into close contact with the laminated polyethylene terephthalate film, and the number of remaining steps after development of the 41-step tablet becomes 26.0. The exposure was performed with the amount of energy. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by weight sodium carbonate aqueous solution was sprayed at 30 ° C. for 30 seconds to remove the unexposed portion and evaluate the adhesion. Adhesiveness is expressed by the width (μm) of the line that remains without being peeled off by the developer. The smaller the numerical value of this adhesiveness, the closer the thin line does not peel off from the glass substrate, so it adheres to the glass substrate. , Indicating high adhesion.

<Evaluation of resolution>
A phototool having a 41-step tablet and a phototool having a wiring pattern with a line width / space width of 30/30 to 200/200 (unit: μm) as a negative for resolution evaluation are closely attached to a polyethylene terephthalate film of a laminate. Then, using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM1201 having a high-pressure mercury lamp, exposure was performed with an energy amount such that the number of remaining step stages after development of the 41-step step tablet was 26.0. After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by weight sodium carbonate aqueous solution was sprayed at 30 ° C. for 30 seconds to remove the unexposed portion and evaluate the resolution. Of the space widths in which the unexposed portions were successfully removed by the development process, the smallest width was defined as the resolution. Table 4 shows the obtained results. The smaller the numerical value, the better the resolution.

<Evaluation of chemical resistance>
Using a parallel light exposure machine (manufactured by Oak Manufacturing Co., Ltd.) EXM1201 having a high-pressure mercury lamp lamp from the polyethylene terephthalate side, the remaining step number after development of the 41-step tablet is 26.0 in the laminate. Exposure was performed. After the exposure, the polyethylene terephthalate film was peeled off and placed in a box dryer heated to 160 ° C. for 1 hour, and immersed in water, acetone and an acidic solvent (H ₂ SO ₄ aqueous solution, concentration 1.0 mol / L) for 1 hour. At this time, the case where there was no peeling was indicated as ◯, the case where it was slightly peeled was indicated as Δ, and the case where it was completely peeled was indicated as x.

(Experimental example 7)
[Preparation of microchemical chip 1]
Using the photosensitive film of Experimental Example 1, laminating, exposing and developing on a glass substrate (Pyrex glass (registered trademark); length 60 mm, width 50 mm, thickness 0.5 mm) under the above conditions, photocuring After forming a product pattern (thickness 40 μm, flow path width 100 μm), a cover glass (Pyrex glass (registered trademark); length 60 mm, width 50 mm, thickness) in which a through hole for introducing a sample is previously formed on the photocured product pattern 0.5mm), and the temperature of the glass substrate and the cover glass is heated to 120 ° C with a vacuum pressure laminator (MVLP-500 manufactured by Meiki Seisakusho), the vacuuming time is 20 seconds, the pressure time is 60 seconds, the pressure Crimping was performed at 0.5 MPa. And it heated and joined at 160 degreeC for 1 hour, and the microchemical chip was produced.

(Experimental Example 8 , Reference Examples 9-12)
[Preparation 2-6 of microchemical chip]
A microchemical chip was produced in the same manner as in Experimental Example 7 except that the photosensitive films of Experimental Example 2 and Reference Examples 3 to 6 were used.
About the obtained microchemical chip | tip, the adhesive strength of a cover glass and a photocured material pattern was evaluated.
<Evaluation of adhesive strength between insulating substrate (lid glass) and photocured material pattern>
For the microchemical chips produced in Experimental Examples 7 and 8 and Reference Examples 9 to 12, Bondester series 4000 (manufactured by DAGE) was used, and the load of 20 kg weight was applied to the insulating substrate (lid glass) and the photocured material pattern. The adhesive strength was evaluated. The evaluation results are shown in Table 3. It shows that adhesive strength is so strong that a numerical value is large.

(Experimental example 13)
[Preparation of microchemical chip 7]
Using the photosensitive film of Experimental Example 1, lamination, exposure and development were performed on a glass substrate (soda glass; length 60 mm, width 50 mm, thickness 1.5 mm) under the above conditions, and a photocured product (resist). A pattern was formed. Thereafter, the glass substrate on which the photocured material pattern is formed is heated at 160 ° C. for 1 hour, and the glass substrate on which the photocured material pattern is formed is immersed in a container containing 25% by volume of a hydrofluoric acid aqueous solution. While stirring with a stirrer, the underlying glass substrate was etched using the photocured material pattern as a mask to form grooves in the glass substrate. Thereafter, the photocured product pattern is peeled off, and a cover glass (soda glass) is bonded to the surface of the glass substrate having a groove by known heat fusion (600 ° C. or higher) to produce a microchemical chip.

It is a perspective view of the board | substrate for microchemical chips in which the hardened | cured material (resist) pattern was formed. It is a perspective view of the insulating base material provided with the through hole. It is a perspective view which shows an example of the microchemical chip using the photosensitive resin composition of this invention. It is sectional drawing which shows an example of the microchemical chip using the photosensitive resin composition of this invention. It is sectional drawing which shows an example of the microchemical chip formed using the photosensitive resin composition of this invention. It is a perspective view of the board | substrate for microchemical chips which formed the groove | channel by etching using a hardened | cured material (resist) pattern as a mask. It is a perspective view which shows an example of the microchemical chip formed using the photosensitive resin composition of this invention.

Explanation of symbols

1: insulating base material 2: photocured material pattern 3: substrate for microchemical chip 4: through hole 5: photosensitive resin composition removing portion (flow path)
6: Microchemical chip 12: Resist pattern 13: Microchemical chip substrate 15: Photosensitive resin composition removing portion 16: Microchemical chip 17: Groove (flow path)

Claims (8)

A photosensitive resin composition for forming a flow path of a microchemical chip, wherein the photosensitive resin composition comprises (A) a binder polymer containing a carboxyl group , (B) a photopolymerizable compound, and (C ) A photopolymerization initiator, and the (B) photopolymerizable compound contains a photopolymerizable compound having at least one unsaturated group in the molecule and at least one hydroxyl group and isocyanuric ring structure in the molecule. A photosensitive resin composition that can be developed with a dilute alkaline aqueous solution . Photosensitive film comprising a support, and the support a photosensitive resin composition composed of a photosensitive resin composition according to claim 1 Symbol placement formed on layer. On a substrate, the photosensitive resin composition of claim 1 Symbol placement, or laminating a photosensitive resin composition layer using a photosensitive film as claimed in claim 2, wherein a predetermined portion of the photosensitive resin composition layer A method for producing a microchemical chip, comprising a step of photocuring an exposed portion by irradiating an actinic ray and a step of forming a photocured product pattern by removing an unexposed portion. Furthermore, the manufacturing method of the microchemical chip of Claim 3 including the process of adhere | attaching the insulating base material which has a through-hole on the said photocured material pattern. On a substrate, the photosensitive resin composition of claim 1 Symbol placement, or laminating a photosensitive resin composition layer using a photosensitive film as claimed in claim 2, wherein a predetermined portion of the photosensitive resin composition layer Irradiating actinic rays to photocuring the exposed portion, removing the unexposed portion to form a photocured product pattern, and etching the substrate using the photocured product pattern as a mask to provide a groove in the substrate The manufacturing method of the microchemical chip characterized by including a process. 6. The method for producing a microchemical chip according to claim 5 , further comprising a step of peeling the photocured product pattern and a step of bonding an insulating base material having a through hole to the surface of the substrate provided with the groove. A microchemical chip comprising a substrate, a flow path pattern laminated on the substrate, and an insulating base material laminated on the flow path pattern, wherein the flow path pattern cures the photosensitive resin composition according to claim 1. A microchemical chip, wherein the substrate and the flow path pattern are bonded, and the flow path pattern and the insulating base material are bonded. A microchemical chip comprising a substrate having a groove serving as a flow path and an insulating base material laminated on the surface of the substrate having the groove, wherein the groove is formed by etching the substrate using the flow path pattern as a mask. a pattern flow path pattern is formed by curing a photosensitive resin composition, and wherein the photosensitive resin composition, provided on a substrate by using a photosensitive film as claimed in claim 2, wherein Micro chemical chip to do.

Images