JP2005227223A - Chip substrate for inspection element and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chip substrate for an inspection element superior in the productivity of water, can be subjected to incineration treatment and capable of reducing the cost required in production and waste treatment, and to provide its manufacturing method. <P>SOLUTION: The chip substrate for the inspection element is a molded product, comprising a cycloolefin-based resin and has minute capillary flow channels or a recessed pattern on its surface. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a chip substrate for a test element known as a so-called biochip, which is used for medical tests or food tests, and more particularly, to a microfabricated mold using a cyclic olefin resin. A chip substrate for a test element having a simple capillary flow path or a concave pattern, which is manufactured by molding a cyclic olefin resin by an injection molding method or a melt casting method. The present invention relates to a chip substrate for an inspection element that has excellent sterilization resistance and can be incinerated after use.

In medical and food inspections, many chemical and biochemical techniques are applied on a single substrate, and the separation, extraction, reaction, and judgment processes necessary for analysis are performed on a single chip. Therefore, a test element capable of satisfying attention has been attracting attention as a so-called biochip. For these inspection elements, a substrate on which microcapillaries, depressions, etc. are arranged is used (for example, Patent Documents 1 to 4).
Conventionally, materials such as glass and silicon are used for these substrates, and techniques such as etching using a photoresist technique are used for pattern formation as described above.
However, substrates manufactured from these materials are difficult to mass-produce and cannot be incinerated after use, resulting in high costs for manufacturing and disposal, and there has been a problem with the widespread use of test elements as described above. .
JP 2002-125654 A JP 2002-131220 A Japanese Patent Laid-Open No. 2002-286643 Japanese Patent Laid-Open No. 2003-021635

  The present invention provides a chip substrate for an inspection element that is excellent in mass productivity and can be incinerated, and can reduce costs for manufacturing and disposal, and a manufacturing method thereof. The present invention provides a chip substrate for a test element having a bactericidal resistance equivalent to the conventional one using a cyclic olefin resin having excellent properties and a method for producing the same.

  As a result of diligent studies to solve the above problems, the present inventors have formed a minute capillary channel or a concave pattern on the surface of the obtained molded product when molded by a specific injection molding method using a cyclic olefin resin. It can be formed, and the transferability of the capillary flow path or the concave pattern is very good, so it is comparable to conventional chip substrates for test elements, and general sterilization methods such as sterilization and radiation sterilization are available. The present invention has been completed by finding that it can be applied and is incinerated because it is made of resin. In other words, by using at least one of a method for reducing the cavity pressure and an injection compression molding method using a mold having a minute capillary channel or a concave pattern, an injection molding method with excellent mass productivity. The present invention has been completed by finding that a molded product that can accurately transfer the pattern of a mold even after production is useful as a chip substrate for an inspection element.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to obtain the chip | tip board | substrate for test | inspection elements which was excellent in sterilization resistance and the pattern formation property, and excellent in surface workability and adhesiveness. The chip substrate for a test element of the present invention is suitable as a biosensor or a chemical sensor used for food or medical tests.

A cyclic olefin resin is used for the chip substrate for the test element of the present invention (hereinafter referred to as “chip substrate”). Examples of the cyclic olefin resin include the following (co) polymers. It is done.
(1) A ring-opening polymer of a specific monomer represented by the following general formula (I).
(2) A ring-opening copolymer of a specific monomer represented by the following general formula (I) and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclization of the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction and then hydrogenation.
(5) A saturated copolymer of a specific monomer represented by the following general formula (I) and an unsaturated double bond-containing compound.
(6) Addition type (co) of one or more monomers selected from a specific monomer represented by the following general formula (I), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentadiene-based monomer Polymers and their hydrogenated (co) polymers.
(7) An alternating copolymer of a specific monomer represented by the following general formula (I) and an acrylate.

[In formula, R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, respectively, and may be same or different, respectively. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a single ring or A polycyclic structure may be formed. m is 0 or a positive integer, and p is 0 or a positive integer. ]

<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.
These can be used alone or in combination of two or more.

Among the specific monomers, in general formula (I), R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms. R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group, and m is 0 An integer of ˜3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer in which m = 1 and p = 0 is preferable in that the cyclic olefin resin obtained has a high glass transition temperature and excellent mechanical strength.
Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups are connected via a linking group such as a methylene group. May be combined. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer having n of 0 is It is preferable in that the synthesis is easy.

In the general formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly a methyl group. In particular, it is preferable that the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity can be lowered.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.
The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer are metathesis It is carried out in the presence of a catalyst.
This metathesis catalyst comprises (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond. In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ , MoCl ₆ , ReOCl _3, etc. JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right page. The compounds described in column 17th line can be mentioned.
(B) Specific examples of the _{component, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like can be mentioned compounds described in JP-A No. 1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3.
As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. The range is preferably 1: 1,000 to 1: 10,000.
The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio.
The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. The

<Solvent for polymerization reaction>
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane, decane, Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, Compounds such as halogenated alkanes and aryl halides such as chloroform and tetrachloroethylene, saturated carbohydrates such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane Esters, dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used singly or in combination. Of these, aromatic hydrocarbons are preferred.
As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable.
These molecular weight regulators can be used alone or in admixture of two or more.
The amount of the molecular weight regulator used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

  (2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.

Although the ring-opening (co) polymer obtained as described above can be used as it is, (3) the hydrogenated (co) polymer obtained by further hydrogenation is a resin having high impact resistance. It is useful as a raw material.
<Hydrogenation catalyst>
In the hydrogenation reaction, a hydrogenation catalyst is added to a usual method, that is, a solution of a ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C., preferably 20 It is carried out by operating at ~ 180 ° C.
As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include heterogeneous catalysts and homogeneous catalysts.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. The homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its characteristics deteriorate due to heating during molding and use as a product. There is no. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. is there. The higher the hydrogenation rate, the better the stability to heat and light, and when used as the wave plate of the present invention, stable characteristics can be obtained over a long period of time.
The hydrogenated (co) polymer used as the cyclic olefin resin of the present invention preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less. It is particularly preferable that the amount is not more than% by weight.

In addition, as the cyclic olefin-based resin of the present invention, (4) a (co) polymer obtained by cyclizing the ring-opened (co) polymer of the above (1) or (2) by a Friedel-Craft reaction and then hydrogenating it. Can be used.
<Cyclization by Friedel-Craft reaction>
The method for cyclizing the ring-opened (co) polymer of (1) or (2) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. Any known method can be employed. Specifically, Lewis acids such as AlCl 3, BF 3, FeCl 3, Al 2 O 3, HCl, CH 3 ClCOOH, zeolite, activated clay, and Bronsted acid are used as the acidic compound.
The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the ring-opening (co) polymer (1) or (2).

Furthermore, as the cyclic olefin resin of the present invention, (5) a saturated copolymer of the specific monomer and an unsaturated double bond-containing compound can also be used.
<Unsaturated double bond-containing compound>
As an unsaturated double bond containing compound, ethylene, propylene, butene etc., Preferably it is C2-C12, More preferably, C2-C8 olefin type compound can be mentioned.
The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.

In the present invention, in order to obtain a saturated copolymer of (5) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.
<Addition polymerization catalyst>
As the catalyst for synthesizing the (5) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a promoter are used.
Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as a vanadium compound, general formula VO (OR) _a X _b or V (OR) _c X _d
[Wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3, ≦ (c + d) ≦ 4. ]
Or an electron-donating adduct of these compounds.
Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.
In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Moreover, adjustment of the molecular weight of the (5) saturated copolymer obtained is normally performed using hydrogen.

Furthermore, as the cyclic olefin resin of the present invention, (6) an addition type of one or more monomers selected from the above specific monomer and a vinyl cyclic hydrocarbon monomer or a cyclopentadiene monomer Copolymers and their hydrogenated copolymers can also be used.
<Vinyl cyclic hydrocarbon monomer>
Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3- Styrenic monomers such as styrene styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene, vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, 4-vinylcycloheptane, 4-isopropenylcycloheptane, etc. And vinyl cycloheptane monomers. Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

<Cyclopentadiene monomer>
Examples of the cyclopentadiene monomer used as the monomer of the addition copolymer (6) of the present invention include, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, Examples include 5-methylcyclopentadiene and 5,5-methylcyclopentadiene. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (5) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the unsaturated double bond-containing compound.
The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the above (3) ring-opening (co) polymer. .

Furthermore, as the cyclic olefin resin of the present invention, (7) an alternating copolymer of the specific monomer and acrylate can also be used.
<Acrylate>
Examples of the acrylate used in the production of the (7) alternating copolymer of the specific monomer and acrylate of the present invention include straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate. C2-C20 heterocyclic group-containing acrylates such as chain, branched or cyclic alkyl acrylates, glycidyl acrylates, 2-tetrahydrofurfuryl acrylates, and aromatic ring groups containing 6-20 carbons such as benzyl acrylates Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as acrylate, isobornyl acrylate, and dicyclopentanyl acrylate.

In the present invention, (7) In order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The polymer is radically polymerized at a ratio of 45 to 55 mol and acrylate of 55 to 45 mol.
(7) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.
The “alternate copolymer” as used herein refers to a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure as a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin used in the present invention is 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl in terms of intrinsic viscosity [η] inh. The polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 12, The weight average molecular weight (Mw) is 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000. It is.
The intrinsic viscosity [η] inh, number average molecular weight and weight average molecular weight are in the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin and the chip substrate of the present invention were used. The molding processability at the time becomes good.

  The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 130 ° C. or higher, preferably 130 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. When Tg is less than 130 ° C., it is not preferable because it is deformed by secondary processing such as sterilization or coating of the substrate. On the other hand, when Tg exceeds 350 ° C., the molding process becomes difficult, and the possibility that the resin deteriorates due to heat during the molding process increases.

When the cyclic olefin-based resin used in the present invention is used as a chip substrate, it is preferable that there are few foreign substances that cause an error in inspection and the like is not present as much as possible.
The content of such foreign matter is preferably 0/10 g of foreign matters of at least 50 μm or more, preferably 0/10 g of foreign matters of 30 μm or more, particularly preferably 0/10 g of foreign matters of 20 μm or more.
The amount of foreign matter is measured by counting the size and number by dissolving the resin in a solvent having solubility of the cyclic olefin resin of the present invention such as toluene and cyclohexane, filtering through a filter, and observing with a microscope. Is done. Similarly, it is possible to count using a commercially available fine particle counter based on the principle of light scattering using a sample in which a resin is dissolved in a solvent having a resin solubility.
It is also preferable to suppress the content of fine powder made of the same material as the cyclic olefin resin used in the present invention as much as possible. A large amount of fine powder is not preferable because it causes an error in inspection.

  For the cyclic olefin-based resin, a specific hydrocarbon-based resin described in, for example, Japanese Patent Application Laid-Open Nos. 9-221577 and 10-287732, or a known heat can be used without departing from the effect of the present invention. Plastic resins, thermoplastic elastomers, rubber polymers, organic fine particles, inorganic fine particles and the like may be blended.

  The cyclic olefin resin of the present invention includes known antioxidants such as 2,6-di-tert-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-tert-butyl- 5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy- It can be stabilized by adding 4-methoxybenzophenone or a benzyl malonate compound. Further, additives such as a lubricant can be added for the purpose of improving processability.

Next, the chip substrate of the present invention will be described.
The chip substrate of the present invention includes a microcapillary array for performing mixing, separation, extraction, filtration, adsorption, chemical reaction, biological reaction, flow, storage, etc. for inspection, and the above-mentioned cyclic olefin. It is formed on a molded product of a resin, and becomes a test element in combination with other chemical and biological elements and test parts.

When the chip substrate of the present invention is of a capillary array type, it is composed of a plurality of spots for performing physical or chemical unit operations on the substrate and capillaries connecting them. In the spot portion, chemical substances, enzymes, or biopolymers such as DNR, RNA and protein are immobilized for inspection, and various reactions, separation, extraction and the like are performed. In addition to the function of transferring the liquid to be inspected, unit operation functions such as separation, adsorption, and filtration can be added to the capillary section.
The size of the chip substrate is usually a rectangular shape of 10 to 200 mm, a width of 10 to 50 mm, and the thickness can be appropriately selected depending on the purpose, but is usually appropriately selected from 0.5 to 5 mm. .
The spot portion is usually a concave shape on a cylinder, a rectangular parallelepiped, or a spherical body, and the shape is appropriately selected depending on the purpose. In general, the depth is 0.001 to 3 mm for the purpose of a storage tank to be inspected, and is appropriately selected within a range not exceeding the thickness of the inspection chip. In the case of 0.1 to 10 mm and a rectangular parallelepiped shape, the width is 0.1 to 5 mm and the length is 0.5 to 5 mm. In addition, when various unit operations are intended, the depth is appropriately selected in the range of 0.1 to 100 μm, and in the case of a cylindrical shape, the dimensions are 0.5 to 5 mm in diameter and a rectangular parallelepiped shape. In some cases, the width is 0.1 to 5 mm and the length is 0.5 to 5 mm.
The shape of the capillary portion can be appropriately selected from a rectangular shape, a semi-cylindrical shape, a V-shape, and the depth is usually 1 to 300 μm and the width is 1 to 300 μm.

  When the chip substrate of the present invention is a microarray type, a plurality of inspections are performed on a single chip, and therefore, the shape of minute inspection spots is arranged on a single chip substrate. As the inspection spot, a known shape such as a cylindrical shape, a spherical shape, a shell shape, a capillary shape in the depth direction, a polygonal column shape, a conical shape, a polygonal pyramid shape, a truncated cone shape, or a polygonal frustum shape is appropriately selected. Is possible. In addition, a pattern for immobilizing chemical substances, biochemical polymers, enzymes, or the like may be formed on the inspection spot. The diameter of the opening or the length of one side of these spots is 10 to 700 μm, and the depth is appropriately selected according to the purpose in the range of 1 to 500 μm.

  The above chip substrate uses an injection molding method or a cavity in which at least one of a method of reducing the cavity and an injection compression molding method is used, using a mold having a minute capillary channel or a concave pattern. Manufactured by a method combining pressure reduction and injection compression molding.

In the method of molding by reducing the pressure inside the mold cavity, the preferable degree of reduced pressure in the present invention is a gauge pressure of -0.08 MPa or less, more preferably -0.09 Pa or less, particularly preferably -0.1 MPa or less. is there. If the gauge pressure exceeds -0.08 MPa, the degree of reduced pressure is insufficient, and the effects described in the present invention cannot be obtained.
In order to achieve these pressure reduction degrees, it is possible to use a vacuum pump of a known method, it is preferable to use a known sealing material such as an O-ring around the cavity and the ejector mechanism, Vacuum grease or the like may be used as long as “contamination” does not occur in the molded product. In addition, the suction port for reducing the pressure can be provided at any location in the mold, but can usually be provided at the ejector mechanism, the end of the sprue and runner, the nested structure, etc. is there. In addition, the vacuum suction sequence may be controlled by an electromagnetic valve or the like in conjunction with the opening and closing of the mold, or may be always operated, and is particularly limited as long as it is a method in which the inside of the cavity has a desired degree of decompression when filled with molten resin. It is not something.
In the molding method in which the cavity is reduced in pressure, since the molten resin is injected in a state where the cavity is closed and the pressure is reduced, an injection delay time is usually set. The injection delay time depends on the capacity of the vacuum pump used and the cavity size, but is usually about 0.5 to 3 seconds.

When injection compression molding is used, when injecting the molten resin, the cavity interval is set to 1.5 to 20 times the thickness of the molded product, and the molten resin is injected there and measured on the cylinder side. A method is used in which the product surface in the mold is compressed to narrow the gap between the cavities while maintaining the pressure of the resin at 200 to 2,000 kgf / cm ² .
Also, keep the mold core in a movable state, leave the core 1.1 to 10 times the thickness of the molded product, inject the molten resin, and after the injection starts or ends, move the movable core to the average speed A method of compressing at a speed of 0.01 mm / sec to 1 mm / sec is also applicable.
These injection compression methods can be performed using a known molding machine.

The injection molding machine used in the present invention may be a known hydraulic drive, electric motor drive, or a hybrid type of these, and is preferably an electric motor drive from the viewpoint of hygiene.
In the plasticizing process of the injection molding machine, an in-line type or a pre-plastic type can be used. In the case of the in-line type, the screw shape such as compression ratio, length / diameter ratio, presence / absence of subflight can be selected as appropriate, and the screw surface is well-known such as chromium-based, titanium-based, nitride-based, carbon-based, etc. It is also possible to apply a coating. It is also possible to provide mechanisms such as screw rotation and pressure control for the purpose of measuring and stability of injection operation. In addition, a method of sealing the cylinder and the hopper portion for storing the molding material with an inert gas such as nitrogen or a method of reducing the pressure is also preferable from the viewpoint of stably obtaining the inspection chip of the present invention.
As the mold clamping mechanism of the injection molding machine, either a direct pressure type or a toggle type can be used. It is also possible to use an injection compression mechanism such as mold clamping compression or core compression, which is preferable.

Known materials and structures of the mold for producing the chip substrate of the present invention can be employed. As preferred materials, ordinary carbon steel, stainless steel, or known alloys based on these are used, and the surface is subjected to quenching treatment or known coating treatment such as chromium, titanium, diamond, nickel-based metal, copper Metal plating for pattern processing such as alloy can be applied.
The pattern formed on the inspection chip may be formed directly on the surface of the metal, plating surface, or stamper using a known processing machine such as an electric discharge machine or a cutting machine, such as electroforming. The pattern may be formed by this method.

The molding conditions of the chip substrate are not particularly limited, but the cylinder temperature is usually 260 ° C. to 350 ° C., and the mold temperature is usually the glass transition temperature Tg-1 ° C. of the cyclic olefin thermoplastic resin to − It is preferable to mold at 40 ° C, preferably in the range of Tg-5 ° C to -25 ° C. The injection speed varies depending on the size of the chip substrate and the cylinder size of the molding machine. For example, when the cylinder diameter is 28 mm, the injection speed is usually 50 mm / sec or more, preferably 60 to 150 mm / sec. Preferably, the holding pressure is adjusted to a minimum pressure and time that can maintain the shape of the molded product.
Moreover, it is preferable to dry and use the cyclic olefin type thermoplastic resin used for this invention previously. A normal hot air dryer or a dehumidifier dryer can be used, but from the viewpoint of the hue of the chip substrate, it is preferable to use a vacuum dryer or a dryer by circulation of an inert gas such as nitrogen.

The chip substrate manufactured by the above method further has functions such as hydrophilicity, hydrophobicity, light transmittance at a specific wavelength, acid resistance, alkali resistance, gas barrier property, antireflection, hard coat, and photocatalytic property as necessary. It is possible to apply a known coating process having
For coating, dry coating methods such as vacuum deposition, sputtering, chemical vapor deposition, etc., or brush coating, roll coating, dipping, spin coating, spraying using a solvent insoluble in the cyclic olefin-based thermoplastic resin of the present invention. It is possible to employ a method such as wet coating in which the coating is performed by a method such as drying with hot air or vacuum, and curing with heat or actinic light depending on the purpose.

The chip substrate of the present invention can be sterilized by a method employed in medical or food applications. As the sterilization method, methods such as autoclave sterilization using high-temperature steam, γ-ray sterilization, and electron beam sterilization can be used.
The cyclic olefin-based thermoplastic resin of the present invention is less deformed by heat in autoclave sterilization, devitrification of the resin by high-temperature steam component, and less distorted and discolored by these active rays in sterilization of gamma rays and electron beams, It can be suitably used as a chip substrate for a test element.

  The chip substrate of the present invention is subjected to treatment such as modification with nucleic acids or enzymes and application / immobilization of reactive chemicals as necessary, and constitutes inspection equipment in combination with other inspection jigs, etc. Therefore, it can be used for medical examinations and food inspections.

Examples of the present invention will be described below, but the present invention is not limited by these examples. In the following, “part” means “part by weight”.
Various measurement methods are described below.
<Intrinsic viscosity: η _inh >
Chloroform was used as a solvent, and measurement was carried out with an Ubbelohde viscometer at a polymer concentration of 0.5 g / dl at 30 ° C.
<Molecular weight>
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of polystyrene were determined by measurement with a tetrahydrofuran (THF) solvent using HLC-8020 gel permeation chromatography (GPC) manufactured by Tosoh Corporation. Here, Mn represents a polystyrene-equivalent number average molecular weight.
<Glass transition temperature: Tg>
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream.

<Cyclic olefin resin>
Synthesis example 1
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (specific monomer) 250 parts, 1-hexene (molecular weight regulator) 41 parts, toluene (ring-opening polymerization solvent) 750 parts in a reaction vessel in which nitrogen was substituted The solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten = 0.20) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / l) of 35 mol: 0.3 mol: 1 mol) was added, and this system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening polymer solution was obtained.
The polymerization conversion rate in this polymerization reaction was 97%.
The autoclave was charged with 4,000 parts of the ring-opening polymer solution thus obtained, and 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.
After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released.
Subsequently, the reaction solution was poured into a large amount of methanol to coagulate and collect the hydrogenated polymer.
Thereafter, the recovered hydrogenated polymer was dissolved in toluene to prepare a solution having a concentration of 20%, filtered through a filter having a pore size of 1 μm, and then poured into a large amount of methanol to coagulate and recover the hydrogenated polymer. . Such re-dissolution / precipitation / recovery was repeated three times, and the finally obtained hydrogenated polymer was dried at 100 ° C. under reduced pressure for 12 hours.
The hydrogenation rate of the thus obtained hydrogenated polymer (hereinafter referred to as “cyclic olefin-based resin A”) was measured by ¹ H-NMR at 400 MHz to be substantially 100%.
Η _inh of the cyclic olefin resin A was 0.52, Mw was 75,000, Mw / Mn was 3.5, and Tg was 164 ° C.

Synthesis example 2
As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] -3-dodecene 225 parts and bicyclo [2.2.1] hept-2-ene 25 parts, except that the amount of 1-hexene (molecular weight regulator) added was 43 parts Obtained a hydrogenated polymer in the same manner as in Synthesis Example 1. The hydrogenation rate of the obtained hydrogenated polymer (hereinafter referred to as “cyclic olefin resin B”) was substantially 100%.
Η _inh of the cyclic olefin resin B was 0.50, Mw was 62,000, Mw / Mn was 3.5, and Tg was 141 ° C.

Synthesis example 3
As a specific monomer, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that 250 parts of ^1,7,10 ] -3-dodecene (specific monomer) and 750 parts of cyclohexane were used as a solvent for the ring-opening polymerization reaction. The hydrogenation rate of the resulting hydrogenated polymer (hereinafter referred to as “cyclic olefin resin C”) was substantially 100%.
Η _inh of the cyclic olefin resin C was 0.50, Mw was 65,000, Mw / Mn was 3.0, and Tg was 145 ° C.

<Adhesive>
A reaction vessel was charged with 250 parts of distilled water, and 90 parts of butyl acrylate, 8 parts of 2-hydroxyethyl methacrylate, 2 parts of divinylbenzene, and 0.1 part of potassium oleate were added to the reaction vessel. This was stirred with a stirring blade made of polytetrafluoroethylene [manufactured by DuPont, Teflon (registered trademark)]. After replacing the inside of the reaction vessel with nitrogen, the temperature of the system was raised to 50 ° C., and 0.2 part of potassium persulfate was added to initiate polymerization. After 2 hours, 0.1 part of potassium persulfate was further added, the system was heated to 80 ° C., and the polymerization reaction was continued for 1 hour to obtain a polymer dispersion. Subsequently, this polymer dispersion was concentrated using an evaporator until the solid content concentration reached 70%, thereby obtaining an adhesive composed of an aqueous dispersion of an acrylate ester polymer.

Other resins Methacrylic resin: specific gravity = 1.19, Tg = 108 ° C., MFR (260 ° C., 10 kg) = 154 g / 10 minutes Polycarbonate resin: specific gravity = 1.20, Tg = 146 ° C., MFR (260 ° C., 10 kg) = 34 g / 10 minutes

Preparation method of resin The solidified and recovered cyclic olefin-based resin was granulated using a melt extruder to obtain pellets. Prior to molding, the obtained pellets were vacuum-dried under the conditions of 100 ° C. × 4 hr for the A component, 80 ° C. × 4 hr for the methacrylic resin of the other component, and 100 ° C. × 6 hr for the polycarbonate resin, and the gas component was impermeable. Stored in an aluminum bag.

Molding method of test piece
Injection molding method-(1)
Samples used in the following tests were injection molded. The injection molding speed is 100 mm / sec, the cylinder temperature is Tg + 140 to 160 ° C. of the resin, and the mold temperature is Tg−10 to −20 ° C. of the resin.
* SG75M-S (Cylinder diameter 28mm, Clamping 75ton) made by Sumitomo Heavy Industries

Injection molding method- (2): Cavity decompression method A pressure release hole for decompression is provided from a clearance of 10 / 1,000 mm provided around the cavity, and a vacuum pump [G-50S manufactured by Vacuum Kiko Co., Ltd. Using an oil rotary vacuum pump, suction capacity 50 L / min)], the cavity was decompressed to perform injection molding. The degree of decompression of the cabin tea at the start of injection was -0.08 MPa in terms of gauge pressure. The injection molding speed is 100 mm / sec, the cylinder temperature is Tg + 140 to 160 ° C. of the resin, and the mold temperature is Tg−10 to −20 ° C. of the resin.
* SG75M-S (Cylinder diameter: 28mm, mold clamping: 75ton) made by Sumitomo Heavy Industries, Ltd.

Injection molding method-(3): With the cavity of the mold-clamping compression mold expanded to 5 mm, the molten resin is injected and the mold is pressed for 3 seconds while keeping the resin pressure measured on the cylinder side constant. Thus, the cavity spacing was compressed to 1 mm, and after cooling for 20 seconds, the mold was opened to obtain a molded product. The injection molding speed is 100 mm / sec, the cylinder temperature is Tg + 140 to 160 ° C. of the resin, and the mold temperature is Tg−10 to −20 ° C. of the resin.
* TR80S2W molding machine manufactured by Sodick (cylinder diameter 32mm, mold clamping 100ton)

Injection molding method- (4): Molten resin is injected with the movable core of the core compression molding die retracted to 1.5 mm, and the movable core is compressed at an average speed of 0.05 mm / sec from the point of completion of filling. After cooling for 20 seconds, the mold was opened to obtain a molded product. The injection molding speed is 100 mm / sec, the cylinder temperature is Tg + 140 to 160 ° C. of the resin, and the mold temperature is Tg−10 to −20 ° C. of the resin.
* SG75M-S (Cylinder diameter: 28mm, mold clamping: 75ton) made by Sumitomo Heavy Industries, Ltd.

Injection molding method- (5): Combination of cavity decompression method and core compression molding With the movable side core of the mold retracted to 1.5 mm, the pressure is reduced from the 10 / 1,000 mm clearance provided around the cavity. After the pressure of the cavity is reduced using a vacuum pump [G-50S manufactured by Vacuum Kiko Co., Ltd. (oil rotary vacuum pump, suction capacity: 50 L / min)] from the pressure release hole provided for injection, the molten resin is injected and filling is completed. From the time, the movable core was compressed at an average speed of 0.05 mm / sec, cooled for 20 seconds, and then the mold was opened to obtain a molded product.
The degree of decompression of the cabin tea at the start of injection was -0.08 MPa in terms of gauge pressure. The injection molding speed is 100 mm / sec, the cylinder temperature is Tg + 140 to 160 ° C. of the resin, and the mold temperature is Tg−10 to −20 ° C. of the resin.
* SG75M-S (Cylinder diameter: 28mm, mold clamping: 75ton) made by Sumitomo Heavy Industries, Ltd.

* Molded product Molded product A: Capillary array mold shape
See Fig. 1 Molded product B: Microcapillary shape
See Figure 2

The performance required as a chip substrate for inspection was evaluated by the following test method.
<Sterilization resistance>
(1) High-pressure steam sterilization The molded product and purified water were sealed in a pressure-resistant bottle, sterilized in an autoclave under conditions of 121 ° C. × 1 hour, and the specimen after sterilization was observed.
・ Shape change ○-Deformation and cracks are not observed.
Δ- Minute deformation or generation of minute cracks is observed.
X: Large deformation or significant cracking is observed.
・ Transparency change ○-No change is seen.
Δ-Some cloudiness is observed.
X—Devitrified.
(2) Electron beam sterilization After irradiating the test piece with an electron beam at a dose of 40 kGy, the test piece was observed.
・ Shape ○-No cracks are observed.
Δ-Generation of minute cracks.
X—Significant cracks are observed.
-Hue change ○-The decrease in transmittance in the visible light region is less than 5%.
△-5% to 10% decrease in transmittance in visible light region
×-10% or more decrease in transmittance in visible light region

<Transferability>
・ Molded product A
The shape was attached to any 10 depressions in the molded product, and the shape was observed with an SEM. A five-step evaluation was performed with 5 being good and 1 being bad.
・ Molded product B
Each capillary and the pattern part were observed with SEM. A five-step evaluation was performed with 5 being good and 1 being bad.

<Surface workability>
・ Coating method (1)
A film of TiO ₂ having a thickness of 100 nm was formed by vapor deposition on one surface where the shape of the test piece was not formed. The pressure at the time of vapor deposition was 10 ⁻⁴ Torr.
・ Coating method (2)
On one side where the shape of the test piece was not formed, SiO ₂ was deposited to 100 nm by a vapor deposition method. The pressure at the time of vapor deposition was 10 ⁻⁴ Torr.
・ Coating method (3)
On one side where the shape of the test piece was not formed, Au was formed into a film by 100 nm by a vapor deposition method. The pressure at the time of vapor deposition was 10 ⁻⁴ Torr.
・ Coating method (4)
70 parts of vinylidene fluoride and 30 parts of hexafluoropropylene were copolymerized to obtain a polymer having a polystyrene-equivalent number average molecular weight of 4.5 × 10 ⁴ . 70 parts of this polymer and 30 parts of dipentaerythritol hexaacrylate were added to 2,500 parts of methyl isobutyl ketone as a solvent and mixed by stirring for 1 hour to obtain a paint having a concentration of 4% by weight. After coating this paint on the same specimen as the coat (1) by dipping, the solvent is sufficiently evaporated by heating to 60 ° C., and the dose is 3 Mrad using an electron beam irradiation device. Cured by irradiating with electron beam

The film was evaluated as follows.
(1) The film formation state was observed.
(2) The film adhesion state after heating at 100 ° C. for 1 hour was observed.
In the evaluation method, the membrane surface was wiped 10 times with Ben Cotton (manufactured by Asahi Kasei Co., Ltd.), and the surface state was observed.
○: No peeling of the film is observed.
Δ: Small scratches are noticeable.
X: The film is peeled off in a planar shape.

<Adhesiveness>
The following flat plate base material and a test chip substrate were bonded together to evaluate the adhesion.
-Adhesion method The above adhesive is applied to the surface of a release film "Bina sheet" (made by Fujimori Kogyo Co., Ltd.) using a bar coater to form a 6 μm thick coating film. A transfer film was prepared by drying for a minute. Next, the dried coating film of the transfer film was transferred to the surface on which the pattern of the substrate surface was not formed, and further bonded to the target substrate.
-Substrate (1) Soda glass plate (2) SUS plate (3) Flat plate obtained by injection molding of the polymer obtained in Synthesis Example 1-Evaluation method Observed after standing in a dryer at 100 ° C for 100 hours Went.
○ -No change △ -Slight peeling.
×-peeled

As shown in Table 1, bactericidal resistance and transferability were evaluated.

  Comparison between Examples 1 to 17 and Comparative Examples 1 to 10 shows that the test chip substrate of the present invention is excellent in sterilization resistance and transferability.

  The surface workability was evaluated as shown in Tables 2 to 5, and the adhesiveness was evaluated as shown in Tables 6 to 9. The shape of the molded product is A.

  From comparison between Examples 18 to 41 and Comparative Examples 11 to 18, and Examples 42 to 61 and Comparative Examples 19 to 26, it can be seen that the test chip substrate of the present invention is excellent in surface workability and adhesiveness.

  The chip substrate for a test element of the present invention is suitable as a biosensor or a chemical sensor used for food or medical tests.

It is a block diagram of the molded product A which has a capillary array type | mold shape, (a) is a front block diagram, (b) is a side block diagram. It is a block diagram of the molded product B which has a microcapillary shape, (a) is a front block diagram, (b) is a side block diagram in each site | part.

Claims (5)

  A chip substrate for a test element, which is a molded product made of a cyclic olefin resin and has a fine capillary channel or a concave pattern on its surface.   The chip substrate for a test element according to claim 1, which is for a biochip.   The chip substrate for an inspection element according to claim 2, wherein the biochip is used for medical inspection or food inspection.   4. The method of manufacturing a chip substrate for a test element according to claim 1, wherein the chip substrate is manufactured by an injection molding method using a capillary channel or a mold having a concave pattern. The method for producing a chip substrate for a test element according to claim 4, wherein the cavity is formed under reduced pressure and / or produced by an injection compression molding method.