JPH10245466A - Composition for fixing electrode, fixing of electrode, electrode for measuring ion, and oxygen electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for fixing electrode low in water adsorption ratio, capable of accurately measuring dissolved oxygen amount in good reproducibility without depending on using position, and simply forming a bendable electrode. SOLUTION: This curable composition for fixing electrode in provided with 100 pts.wt. (meth)acrylic monomers (i) and 0.1-30 pts.wt. polymer initiator. The oxygen electrode is provided with an outer cylindrical body 10 made of flexible resin, a silver- silver chloride reference electrode 20 and an acting electrode 30 for preparing platinum, mutually separately arranged in the outer cylindrical body 10 in the longitudinal direction, cured bodies 40A and 40B of a composition for fixing electrode packed between these electrodes and the outer cylindrical body 10, electrolytic crystal body made of KCl crystal fixed to either one end face 50 of the outer cylindrical body so as to integrally cover the end faces of these electrodes and a fine pore membrane 80 for integrally covering one end peripheral area 70 of these electrodes, composition cured material and the electrolytic crystal body, and the cured body of the composition is obtained by reacting a composition containing the (meth)acrylic monomers and the polymerization initiator, and curing it.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an electrode fixing composition, an electrode fixing method, an ion measuring electrode (electrode) and an oxygen electrode. More specifically, the present invention has a low water absorption and a good reproducibility regardless of the use site. The present invention relates to an electrode fixing composition, an electrode fixing method, an ion measuring electrode, and an oxygen electrode that can accurately measure the amount of dissolved oxygen and the like and can easily form a flexible electrode.

[0002]

2. Description of the Related Art Conventionally, oxygen electrodes have been widely used not only for medical purposes but also for industrial purposes (as so-called "dissolved oxygen meters"), but most of them are used for fixing electrodes such as noble metal electrodes. In that case, glass was used.

[0003] However, a special technique was required to fix the noble metal electrode to the mating member with glass and to fix the noble metal electrodes to each other. In addition, such a glass fixed electrode (glass electrode) has poor flexibility, and even if it is inserted into a micro blood vessel or the like in order to measure the amount of dissolved oxygen in the blood at the time of surgery or the like, it is broken in the blood vessel. Etc.,
It was difficult to use for such an application.

When the present inventors used, for example, epoxy resin as a substitute for the electrode fixing glass, the obtained epoxy resin fixed electrode (epoxy resin electrode) was
When used in the presence of water for a long time (eg, 1 to 3 weeks), the epoxy resin gradually swells, the surface area of the electrode end surface (detection site) changes, the voltage between the electrodes changes significantly, and the measurement of the amount of dissolved oxygen, etc. Problems have been found to be impossible or difficult.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problems associated with the prior art as described above, and by simply fixing an electrode such as a noble metal electrode to a tube without special technology. It is another object of the present invention to provide an electrode fixing composition that can easily form a flexible electrode (electrode for ion measurement) having a low water absorption.

An object of the present invention is to provide a method of fixing an electrode such as a noble metal electrode to a tube or the like easily without requiring a special technique. The present invention is an ion which can be easily formed, is flexible, has a low water absorption, is hardly affected by moisture in the measurement environment, can accurately measure the dissolved oxygen amount with good reproducibility regardless of the use site. It is intended to provide a measurement electrode and an oxygen electrode.

[0007]

SUMMARY OF THE INVENTION The curable composition for fixing an electrode according to the present invention is characterized by containing a (meth) acrylic acid-based monomer and a polymerization initiator. It is desirable that the polymerization initiator be contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acid monomers.

[0008] In the present invention, the (meth) acrylic acid-based monomer is an acid group-containing monomer in an amount of 1 to 20% by weight.
Is preferable for improving the adhesion to the electrode.

In the method for fixing an electrode according to the present invention, when an electrode such as a noble metal electrode surface-treated with an adhesive metal treating agent is fixed to a counterpart member, the composition described above is interposed between the electrode and the counterpart member. Is fixed by filling and curing.

In the present invention, when the electrode is a noble metal electrode, the noble metal electrode is preliminarily treated with an adhesive primer (eg, an SH group-containing compound, a sulfur compound) before the surface treatment with the adhesive metal treating agent. Surface treatment.

As the above-mentioned adhesive primer, a 1,3,5-triazine-2,4-dithione derivative containing a polymerizable double bond represented by the following formula (I) or (II):
1, containing a polymerizable double bond represented by I) or (IV)
An adhesive metal treating agent containing any triazine-based compound among 3,5-triazine-2,4-dithiol derivatives is preferable.

[0012]

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[0013]

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[0014]

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[0015]

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(In the formulas (I) to (IV), n is 1 to 8, Y is oxygen or sulfur, R is an alkyl or allyl group having 1 to 8 carbon atoms, and Z is

[0017]

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Any of the above). An electrode for ion measurement (ion sensor) according to the present invention comprises an outer cylinder made of a flexible resin formed in a substantially cylindrical shape, and a distance from each other in the outer cylinder along the longitudinal direction of the outer cylinder. The reference electrode and the working electrode arranged as described above, a cured body of the electrode fixing composition filled between these electrodes and the outer cylinder, and one end face of the outer cylinder, an end of these electrodes And a microporous membrane that integrally covers one end outer peripheral region of the electrode, the cured body of the electrode fixing composition, and the electrolyte crystal. .

In particular, when the electrode for ion measurement according to the present invention is used as an electrode for oxygen content measurement, the oxygen electrode comprises an outer cylindrical body made of a flexible resin formed in a substantially cylindrical shape. A silver-silver chloride reference electrode and a platinum working electrode disposed apart from each other in the outer cylinder along the longitudinal direction of the outer cylinder, and filled between these electrodes and the outer cylinder. A cured body of the electrode fixing composition, an electrolyte crystal made of a KCl crystal fixed to one end face of the outer cylinder so as to integrally cover the ends of the electrodes,
A cured product of the electrode-fixing composition and a microporous membrane that integrally covers one outer peripheral area of the electrolyte crystal; and the cured product of the electrode-fixing composition is polymerized with (meth) acrylic acid-based monomers. It is preferable that the composition containing an initiator is reaction-cured.

When the reference electrode and the working electrode are surface-treated with an adhesive metal treating agent containing any of the triazine compounds of the formulas (I) to (IV), the cured electrode fixing composition This is preferable because it can impart adhesiveness to (resin) and improve the machining accuracy of the electrode.

According to the present invention, there is provided an electrode fixing composition which has a low water absorption, enables accurate measurement of oxygen content and the like with good reproducibility irrespective of the use site, and can easily form a flexible electrode. Can be provided.

According to the method for fixing an electrode according to the present invention, the composition such as a noble metal electrode can be easily fixed by filling and applying the composition between the electrode and a mating member such as a tube.

The above-mentioned ion sensor (electrode for measuring ions), particularly the oxygen electrode, according to the present invention has a low water absorption and can measure the amount of dissolved oxygen and the like in a place having a large amount of water. The sensor can flexibly measure the amount of oxygen or the like with good accuracy, and the sensor is flexible. Such an electrode (ion sensor) can be easily manufactured.

[0024]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the curable composition for fixing an electrode, the method for fixing an electrode, the electrode for measuring ions, and the electrode for measuring oxygen content according to the present invention will be described in detail.

[Curable Composition for Fixing Electrodes] The curable composition for fixing electrodes according to the present invention (also referred to simply as “curable composition”) comprises a (meth) acrylic acid-based monomer, a polymerization initiator and It contains.

Such a curable composition preferably has a small amount of shrinkage upon curing and a small water absorption after curing. The cured composition has a water absorption of 10% by weight or less, and more preferably 5% by weight. % Is desirable.

<(Meth) acrylic acid-based monomer> The (meth) acrylic acid-based monomer used in the present invention has a polymerizable group. Examples of such a polymerizable group include (meth) Acryloyl group, styryl group, vinyl group,
Examples thereof include radically polymerizable unsaturated groups having an allyl group or the like. In addition, when referring to (meth) acrylic acid-based monomers, in addition to the following (meth) acrylic acid-based polymerizable monomers [A], among the (meth) acrylic acid-based monomers described below, a hydroxyl group-containing monomer [B] ] And [B] and [C], and in particular, these (meth) acrylic acid-based monomers having no polar group are used as polymerizable monomers. They are referred to as [A], [A] component and the like.

The (meth) acrylic acid monomers used in the present invention may contain at least one group selected from the above polymerizable groups in one molecule (the (meth) acrylic monomer described below). All polymerizable groups in a polymerizable monomer, including acid-based monomers, should be construed similarly.) <Polymerizable monomer [A]> These polymerizable monomers [A] further include a carboxyl group (or a carbonyloxy group or a carbonyl group), a phosphoric acid group, a sulfonic acid group, a hydroxyl group, an amino group, and a glycidyl group. It can contain functional groups such as groups.

The polymerizable monomer [A] used in the present invention
As, for example, methyl (meth) acrylate, (meth)
Aliphatic esters of (meth) acrylic acid such as ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate; ethylene glycol Di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, etc. Polyethylene glycol di (meth) acrylates; propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate Rate, polypropylene glycol di (meth) acrylates such as nonapropylene glycol di (meth) acrylate; one of the above-mentioned polyethylene glycol di (meth) acrylate and polypropylene glycol di (meth) acrylate has a (meth) acryloyl group Mono (meth) acrylates substituted with a methyl group or an ethyl group; 2- (meth) acryloyloxyethyl isocyanate or 2,2,4-trimethylhexamethylene diisocyanate or 1,3,5-trimethylhexamethylene diisocyanate and 2 (Meth) acrylates having a urethane bond such as an adduct of hydroxyethyl (meth) acrylate; (meth) acrylic acid is further condensed with a product obtained by adding oxyethylene to bisphenol A. It was 2,2
-Bis (4- (meth) acryloyloxypolyethoxyphenyl) propanes; styrene derivatives such as styrene, 4-methylstyrene, 4-chloromethylstyrene and divinylbenzene; and vinyl acetate. These polymerizable monomers can be used alone or in combination.

The above polymerizable monomers [A] can be used alone or in combination. <Hydroxyl-containing polymerizable monomer [B]> The curable composition according to the present invention includes a polymerizable monomer [B] having a hydroxyl group in the molecule (hereinafter referred to as “hydroxyl-containing polymerizable monomer [B]”, “[ B] component)). Examples of the polymerizable group include the same as those described above. Such a hydroxyl-containing polymerizable monomer further contains a functional group such as a carboxyl group (or a carbonyloxy group or a carbonyl group), a phosphoric acid group, a sulfonic acid group, an amino group, and a glycidyl group in the molecule. You can also.

Among the hydroxyl group-containing polymerizable monomers [B], as the monomer having a (meth) acryloyl group, which is a kind of a carboxyl group, a carbonyloxy group or a carbonyl group-containing group, specifically, for example, Hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxydecyl ( (Meth) acrylate, 1,2- or 1,3- and 2,3-dihydroxypropane (meth) acrylate, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) A Relate, pentaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, polypropylene glycol mono ( (Meth) acrylate, 1,3- or 2,3-
Hydroxyl-containing (meth) acrylates such as dihydroxypropyl (meth) acrylate; methylol (meth) acrylamide, N- (meth) acryloyl-2,
Hydroxyl-containing (meth) acrylamides such as 3-dihydroxypropylamine and N- (meth) acryloyl-1,3-dihydroxypropylamine; 2-hydroxy-3-phenoxypropyl (meth) acrylate (in the case of methacrylate, HPPM); Addition product of 2-hydroxy-3-naphthoxypropyl (meth) acrylate (HNPM for methacrylate), 1 mol of bisphenol A and 2 mol of glycidyl (meth) acrylate (GMA for methacrylate) (Bis for methacrylate) -GMA) and an addition product of GMA and an aliphatic or aromatic polyol (including phenol).

The component [B] includes, for example, 2
-Hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 10-hydroxy Decyl (meth) acrylate, diethylene glycol mono (meth)
Acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (Meth) acrylate, polypropylene glycol mono (meth) acrylate, 1,3- or 2,3-dihydroxypropyl (meth) acrylate, N- (meth) acryloyl-
2,3-dihydroxylpropylamine, N- (meth)
Acryloyl-1,3-dihydroxylpropylamine and the like can be mentioned.

Of these polymerizable monomers, 2-hydroxyethyl (meth) acrylate (HEMA in the case of methacrylate) is particularly preferred. In the present invention, these hydroxyl group-containing monomer components [B] can be used alone or in combination.

In the present invention, the curable composition may further contain a polymerizable monomer such as maleic acid and p-vinylbenzoic acid. <Acid group-containing monomer [C] component> The curable composition according to the present invention may contain a polar group-containing monomer such as an acid group-containing monomer (hereinafter, also referred to as “[C] component”). Good. Such a polar group-containing monomer (acidic group-containing monomer and hydroxyl group-containing monomer) contributes to an improvement in adhesion to a metal. However, when used in an excessively large amount (e.g., 20% by weight or more in each of (meth) acrylic acid-based monomers ([A] + [B] + [C])), the water absorption of the cured product increases, and the cured product swells. Because of the danger, it is desirable that the amount of each of the (meth) acrylic acid-based monomers be 20% by weight or less, more preferably 10% by weight or less.

Examples of such an acidic group include a carboxylic acid group (including a carbonyloxy group: -COO-; the same applies hereinafter), a phosphoric acid group, a thiophosphoric acid group, a sulfonic acid group, a sulfinic acid group, and the like. Can be. In this specification, for example, a carboxylic acid group and a carbonyloxy group (—COO—) may be simply referred to as a carboxylic acid group or a carboxyl group.

Among the acidic group-containing monomers [C], (meth) acrylic acid monomers having at least one carboxyl group, carbonyloxy group or carbonyl group in one molecule include monocarboxylic acid, dicarboxylic acid, Tricarboxylic acids and tetracarboxylic acids or derivatives thereof can be mentioned.

Specific examples of the carboxyl group, carbonyloxy group or carbonyl group-containing (meth) acrylic acid-based monomers include (meth) acrylic acid and 11- (meth) acryloyloxy-1,1 −
Undecanedicarboxylic acid (for methacrylate: MA
C-10) 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxyethylnaphthalene-1,2,6-tricarboxylic acid, 4-
(Meth) acryloyloxymethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxyethyl trimellitic acid (for methacrylate: 4-MET)
And its anhydride (in the case of methacrylate: 4-MET
A), 4- (meth) acryloyloxybutyl trimellitic acid and its anhydride, 4- [2-hydroxy-3-
(Meth) acryloyloxy] butyl trimellitic acid and its anhydride, 2,3-bis (3,4-dicarboxybenzoyloxy) propyl (meth) acrylate, N,
O-di (meth) acryloyloxytyrosine, O- (meth) acryloyloxytyrosine, N- (meth) acryloyloxytyrosine, N- (meth) acryloyloxyphenylalanine, N- (meth) acryloyl p-aminobenzoic acid, N -(Meth) acryloyl O-aminobenzoic acid, N- (meth) acryloyl 5-aminosalicylic acid (for methacrylate: 5-MASA), N- (meth) acryloyl 4-aminosalicylic acid, 2 or 3 or 4- (meth) ) Addition product of acryloyloxybenzoic acid, 2-hydroxyethyl (meth) acrylate and pyromellitic dianhydride (for methacrylate: PMD
M), 2-hydroxyethyl (meth) acrylate and maleic anhydride or 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (in the case of methacrylate: BT
DA) or an addition reaction product of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2- (3,4-dicarboxybenzoyloxy) 1,3-di (meth) acryloyloxypropane, N Adduct of phenylglycine or N-tolylglycine with glycidyl (meth) acrylate, 4-[(2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid, 3 or 4-
[N-methyl N- (2-hydroxy-3- (meth) acryloyloxypropyl) amino] phthalic acid and the like can be mentioned. Among them, MAC-10, 4-M
ET, 4-META and 5-MASA are preferably used. These carboxyl group, carbonyloxy group or acidic group-containing monomers containing a carbonyl group can be used alone or in combination.

As the (meth) acrylic acid-based monomers having at least one phosphoric acid group in one molecule of the acidic group-containing monomer [C], specifically, for example, 2- (meth) acrylic acid monomers
(Meth) acryloyloxyethyl acid phosphate, 2 and 3- (meth) acryloyloxypropyl acid phosphate, 4- (meth) acryloyloxybutyl acid phosphate, 6- (meth) acryloyloxyhexyl acid phosphate, 8- (meth) acryloyl Oxyoctyl acid phosphate, 10-
(Meth) acryloyloxydecyl acid phosphate, 12- (meth) acryloyl oxide decyl acid phosphate, bis {2- (meth) acryloyloxyethyl} acid phosphate, bis {2 or 3- (meth) acryloyloxypropyl} acid phosphate, Examples thereof include 2- (meth) acryloyloxyethyl phenyl acid phosphate and 2- (meth) acryloyloxyethyl p-methoxyphenyl acid phosphate. The phosphate group in these compounds can be replaced by a thiophosphate group.

Of these, 2- (meth) acryloyloxyethylphenylacid phosphate and 10- (meth) acryloyloxydecylacid phosphate are preferably used. Having these phosphate groups (meth)
Acrylic monomers can be used alone or in combination.

Among the acidic group-containing monomers [C], (meth) acrylic acid-based monomers having at least one sulfonic acid group in one molecule include, for example,
2-sulfoethyl (meth) acrylate, 2 or 1-
Sulfo-1 or 2-propyl (meth) acrylate,
1- or 3-sulfo-2-butyl (meth) acrylate, 3-bromo-2-sulfo-2-propyl (meth) acrylate, 3-methoxy-1-sulfo-2-propyl (meth) acrylate, 1,1- Dimethyl-2-sulfoethyl (meth) acrylamide and the like can be mentioned. Among them, 2-methyl-2- (meth) acrylamidopropanesulfonic acid is preferably used. These (meth) acrylic acid monomers having a sulfonic acid group can be used alone or in combination.

The curable composition according to the present invention may contain the above-mentioned acidic group-containing monomer [C]. In this case, the acidic group-containing monomer [C] is replaced with the (meth) acrylic acid System monomers ([A] + [B] + [C]) 10
It may be contained in an amount of 1 to 20% by weight in 0% by weight. When the amount of the acidic group-containing monomer [C] exceeds 20% by weight, the mechanical strength of the obtained cured product tends to decrease.

In the present invention, the above-mentioned component [C] can be used alone or in combination. <Polymerization initiator [D]> Examples of the polymerization initiator [D] contained in the curable composition of the present invention include organic peroxides, inorganic peroxides, and alkylboranes (preferably having an alkyl group having 1 to 1 carbon atoms). 10, and also 1 to 6 trialkylboranes, for example:
Tributylborane (TBB)), partial oxides of alkylboranes, α-diketone compounds, organic amine compounds, organic sulfinic acids, organic sulfinates, inorganic sulfur compounds, and barbituric acids. One or more of these can be used. For convenience, these polymerization initiators can be classified into a room temperature chemical polymerization type, a photopolymerization type, a composite dual type thereof, and the like according to the type of polymerization reaction using the polymerization initiator.

The peroxide (polymerization initiator) used in the room temperature chemical polymerization type includes, for example, diacetyl peroxide, dipropyl peroxide, dibutyl peroxide,
Dicapryl peroxide, dilauryl peroxide, dilauryl peroxide, benzoyl peroxide (BPO),
Organic peroxides such as p, p'-dichlorobenzoyl peroxide, p, p'-dimethoxybenzoyl peroxide, p, p'-dimethylbenzoyl peroxide, p, p'-dinitrodibenzoyl peroxide and ammonium persulfate, potassium persulfate And inorganic peroxides such as potassium chlorate, potassium bromate and potassium perphosphate. Of these, BPO is preferred.

The polymerization initiator used in the photopolymerization type is a polymerization initiator that can be photopolymerized by irradiation with ultraviolet light or visible light. There is no particular limitation on the polymerization initiator that can be used in the photopolymerization, and examples thereof include benzyl, 4,4′-dichlorobenzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, and 9,10-anthraquinone. , Diacetyl, d,
Ultraviolet or visible light sensitizers such as diketone compounds such as 1-camphorquinone (CQ) are included. <Reducing Compound> When polymerization is performed by room temperature chemical polymerization or photopolymerization, an organic or inorganic reducing compound can be used in combination. Here, as the organic reducing compound, for example, N, N-dimethylaniline, N,
N-dimethyl p-toluidine (DMPT), N, N-diethyl p-toluidine, N, N-diethanol p-toluidine (DEPT), N, N-dimethyl p-tert-
Butylaniline, N, N-dimethylanisidine, N, N-
Dimethyl p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid ( DEABA) and its alkyl esters, N, N-dimethylaminobenzaldehyde (D
Aromatic amines such as MABAd); N-phenylglycine (NPG), N-tolylglycine (NTG), N,
N- (3-methacryloyloxy-2-hydroxypropyl) phenylglycine (NPG-GMA) or the like can be used in combination.

Among these, DMPT, DEPT, D
EABA, DMABAd, NPG and NTG can be preferably used. In particular, in order to surely cure the curable composition of the present invention and further improve the adhesiveness to a partner member, the following general formula (a):

[0046]

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[In the formula (a), R ¹ and R ² are each independently a hydrogen atom or an alkyl group which may have a functional group or a substituent, and R ³ is a hydrogen atom or A metal atom] or the following general formula:
(b):

[0048]

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[In the formula (b), R ⁴ and R ⁵ are each independently a hydrogen atom or an alkyl group, and R ⁶ is a hydrogen atom or may have a functional group or a substituent. An alkyl group or an alkoxyl group],
It is preferable to include at least one of the amine compounds represented by

Examples of the amine compound included in the general formula (a) include NPG, NTG and NPG-
GMA and the like can be mentioned. Of these, NPG
Is particularly preferably used.

Examples of the amine compound included in the general formula (b) include N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid (DEABA) and its alkyl ester,
Aliphatic alkylamino represented by N, N-dipropylaminobenzoic acid and its alkyl ester, N, -isopropylaminobenzoic acid and its alkyl ester, N, -isopropyl-N-methylaminobenzoic acid and its alkyl ester Benzoic acid and its alkyl esters; aliphatic alkylaminobenzaldehyde represented by DMABAd, N, N-diethylaminobenzaldehyde, N, N-dipropylaminobenzaldehyde, N, -isopropyl-N-methylaminobenzaldehyde And N, N-dimethylaminoacetylbenzene, N, N-diethylaminoacetylbenzene, N, N
N-dipropylaminoacetylbenzene, N, -isopropylaminoacetylbenzene, N, -isopropyl-
Examples thereof include aliphatic alkylaminoacetylbenzenes represented by N-methylaminoacetylbenzene and the like, and aliphatic alkylaminoacylbenzenes. These amine compounds can be used alone or in combination.

Other organic reducing compounds other than those described above include, for example, benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid acid,
Aromatic sulfinic acids such as naphthalenesulfinic acid or salts thereof can be used in combination.

As the inorganic reducing compound, a sulfur-containing reducing inorganic compound can be preferably used. As such a compound, a reducing inorganic compound used as a redox polymerization initiator that can be used when polymerizing a radical polymerizable monomer in a medium such as water or an aqueous solvent is preferable, for example, sulfurous acid, bisulfite, metasulfite, Metabisulfite, pyrosulfite, thiosulfate, dithionite, 1,
Examples include dithionic acid, hyposulfite, hydrosulfite and salts thereof. Of these, sulfites are preferably used,
Particularly, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, and potassium hydrogen sulfite are preferable. These reducing inorganic compounds can be used alone or in combination.

In the curable composition of the present invention, the polymerization initiator [D] is usually 0.1 to 30 parts by weight, preferably 10 to 10 parts by weight, based on 100 parts by weight of the (meth) acrylic acid-based monomer.
Preferably, it is contained in an amount of 25 parts by weight.

When the amount of the polymerization initiator [D] is less than 0.1 part by weight, curing is insufficient, and when it exceeds 30 parts by weight, mechanical strength tends to be insufficient. Further, the curable composition of the present invention contains the polymerizable monomer [A], the hydroxyl group-containing polymerizable monomer [B], the acidic group-containing monomer [C], and the polymerization initiator [D] per 100 parts by weight in total. Component [A] is 1 to 99.99 parts by weight, component [B] is 0 to 60 parts by weight,
Component [C] is 0 to 10 parts by weight, and component [D] is 0.01 to 10 parts by weight.
It is preferred to contain each in an amount of 50 parts by weight.

More preferably, [A], [B],
Per 100 parts by weight of the total of the components [C] and [D], the curable composition contains the component [A] in an amount of 3 to 90 parts by weight,
It is desirable that the component [B] is contained in an amount of 1 to 50 parts by weight, the component [C] in an amount of 1 to 5 parts by weight, and the component [D] in an amount of 0.1 to 30 parts by weight.

The curable composition of the present invention comprises the above [A],
[E]: At least one filler selected from the group consisting of organic fillers, inorganic fillers, and organic composite fillers can be contained in addition to the components [B], [C], and [D]. (Also referred to as a second curable composition).

Hereinafter, a composition containing the above [A] and [D] (and [B] and [C] as necessary) and not containing the [E] component is referred to as a first curable composition of the present invention. The viscosity of the first and second curable compositions of the present invention measured at 37.5 ° C. using an E-type viscometer (hereinafter simply referred to as “viscosity”) is usually 100 to 30,000 cP. , Preferably 100 to 20,000 cP, more preferably 100 to 20,000 cP.
Desirably, it is 8,000 cP. By using a curable composition having this viscosity range, excellent sealing properties and adhesiveness can be exhibited, particularly, without any gap at the adhesive interface with the partner member.

In the second curable composition of the present invention,
The component [E] is at least one filler selected from organic fillers, inorganic fillers, and organic composite fillers.

Examples of the organic filler include a powder polymer filler obtained by pulverizing or dispersion polymerizing a polymer and a filler obtained by polymerizing a polymerizable monomer containing a crosslinking agent and then pulverizing the polymerized monomer. Here, the polymer as a raw material of the filler that can be used is not particularly limited, but a homopolymer or a copolymer of the polymerizable monomer exemplified as the component [A] or the component [B] is preferably mentioned. Can be. For example, polymethyl methacrylate (PMMA), polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate (PB
MA), polyvinyl acetate (PVAc), polyethylene glycol (PEG) and polypropylene glycol (PP
G) and polyvinyl alcohol (PVA).

As the inorganic filler, for example, silica,
Examples thereof include silica alumina, alumina, alumina quartz, glass (including barium glass), titania, zirconia, calcium carbonate, kaolin, clay, mica, aluminum sulfate, barium sulfate, calcium sulfate, titanium oxide, and calcium phosphate.

[0062] In the second curable composition of the present invention, the component [A] is 1 to 1 based on the total weight of the components [A], [B], [C] and [D]. 99.99% by weight, [B] component is 0 to 60% by weight, and [C] component is 0 to 0%.
10% by weight, the component [D] is 0.01 to 50% by weight, and the component [E] is based on the total weight of the components [A], [B], [C], [D] and [E]. It is desirable to contain it in an amount of 15 to 85% by weight.

The viscosity of the second curable composition of the present invention can be easily changed by adjusting the amount of the component [E].
It can be used after being adjusted within the range of 30,000 cP.

The first and second curable compositions of the present invention are:
The above components [A] to [E] may be pre-mixed and stored, transported, etc., and each component may be singly or divided in an arbitrary combination and stored in a separate container for each unit. It may be stored and transported as a product kit, mixed immediately before use, and provided for electrode fixation.

Specifically, for example, a kit composed of a mixture unit composed of the components [A] / [B] / [C] / [E] and a component unit [D]: A kit composed of a mixture unit of the component [B] / [C] / [E] and a mixture unit of the component [B] (/ [A] / [E]) / [D] may be mentioned.

In the case where the component [D] is, for example, two components consisting of BPO or CQ and an amine,
/ [C] / [D] (BPO or CQ) [A] /
A mixture unit of the component [E], [A] / [B] /
[E] / [D] ｛amines, such as N, N-dimethyl p-
And a kit composed of toluidine (abbreviated as DMPT) and a mixture unit of components.

[Ion Measurement Electrode] Next, the ion measurement electrode according to the present invention (also referred to as an ion sensor or an electrode).
Will be described in detail with reference to the accompanying drawings.

FIG. 1 (a) is a cross-sectional view showing a preferred embodiment of the ion measuring electrode (ion sensor) according to the present invention, and FIG. 1 (b) is an ion measuring electrode shown in FIG. 1 (a). FIG. 3 is a longitudinal sectional view of the electrode for use. FIG. 1A is a cross-sectional view taken along line AA of FIG. 1B. FIG. 2A is a cross-sectional view showing another preferred embodiment of the ion measurement electrode (ion sensor) according to the present invention, and FIG. 2B is an ion measurement electrode shown in FIG. 2A. FIG. FIG. 2 (a) is the same as FIG.
FIG. 3B is a cross-sectional view taken along line BB of FIG.

As shown in FIG. 1, a preferred ion measuring electrode (ion sensor) 1 of the present invention comprises an outer cylindrical body 10 made of a flexible resin formed in a substantially cylindrical shape, and a longitudinal section of the outer cylindrical body. A reference electrode 20 and a working electrode 30 which are arranged apart from each other in the outer cylinder along the direction;
The cured product 40A, 40B (or 40) of the curable composition for fixing the electrode (curable composition for fixing the electrode) filled between the outer cylinder 10 and the outer cylinder 10 Of the electrodes 20, 30 on one end face 50 thereof.
And a cured body 40 of the electrode 20, 30 and the electrode fixing composition.
A and 40B and a microporous membrane 80 that integrally covers the outer peripheral region 70 at one end of the electrolyte crystal body (electrolyte crystal) 60.

The preferred ion measuring electrode 1 of the present invention is:
As shown in FIG. 1 (a), the outer cylinder 10 is
It is preferable to provide a partition body 10A that partitions between the zero and the working electrode 30. As described above, the outer cylinder body 10 is
When 0 A is provided, the two types of electrodes 20 and 30 can be reliably and easily separated from each other in the outer cylinder 10 along the longitudinal direction of the outer cylinder 10, which is preferable. In the present invention, the ion measurement electrode 1 shown in FIG. 2 without such a partition 10A may be used. The diameter and the length of the ion measurement electrode 1 are not particularly limited. For example, the diameter φ of the ion measurement electrode 1 in FIG. 1A is about 0.5 to 2 mm (eg, 1 mm). , The diameter of the reference electrode 20 is 100 to 500 μm (for example, 250 μm).
m), and the diameter of the working electrode 30 is 10 to 100 μm.
m (eg, 25 μm). <Outer cylinder> The outer cylinder (tube) 10 is not particularly limited as long as it is formed of a flexible resin, and nylon, polyurethane, polyester, polyethylene, polyvinyl chloride, polycarbonate, fluororesin, polystyrene and the like are used. And a rubber-based component [for example, a natural rubber or a synthetic rubber-based diene rubber, an olefin-based rubber, a silicone rubber, a urethane rubber, or the like]. Among these, urethane resins having particularly high strength and low water absorption are preferred. The thickness of the outer cylinder 10 can be appropriately changed in design according to the required degree of flexibility, the type of resin, and the like, and is, for example, about 10 to 1000 μm. The water absorption of such an outer cylinder 10 is
It is preferably as low as possible, usually 10% or less, more preferably 5% or less. <Reference Electrode, Working Electrode, and Electrolyte Crystal> The combination of the reference electrode 20, the working electrode 30, and the electrolyte crystal 60 depends on the type of the ion to be measured. Is the reference electrode (silver-silver chloride) /
Electrolyte crystal (KCl crystal) / working electrode (Pt). <Microporous membrane> The microporous membrane 80 is not particularly limited as long as it has a molecule (or ion) permeable pore communicating between the front and back surfaces of the membrane. (Example: urethane resin) increases the adhesive strength between the outer cylindrical body 10 and the microporous membrane 80, and increases the microporous membrane strength, long-term stability of the ion measurement electrode performance, reliability, etc. Is preferred.

The thickness of the microporous membrane 80 is not particularly limited, but is usually 10 to 1000 μm, preferably 50 to 1000 μm.
It is about 200 μm. Next, the ion measurement electrode 1
In particular, the case where it is used as an electrode for oxygen amount measurement (oxygen electrode) will be described in detail below.

[Oxygen Content Measurement Electrode (Oxygen Electrode)]
When the ion measurement electrode 1 (ion sensor) according to the present invention is used as an oxygen electrode, the oxygen electrode is arranged in the outer cylinder along the longitudinal direction of the outer cylinder so as to be separated from each other. Silver-silver chloride reference electrode and platinum working electrode, a cured body of the electrode fixing composition filled between these electrodes and the outer cylinder, and one end face of the outer cylinder, these electrodes An electrolyte crystal made of a KCl crystal fixed so as to integrally cover the ends of the electrode, a cured body of the electrode, the electrode fixing composition, and a microporous membrane integrally covering one outer peripheral area of the electrolyte crystal. Preferably, the cured product of the composition for fixing an electrode is a product obtained by reacting and curing a composition containing a (meth) acrylic acid-based monomer and a polymerization initiator.

[Production of Electrode for Ion Measurement] Next, the production method of the electrode for ion measurement, particularly the oxygen electrode, will be described in detail. <Surface Treatment of Electrode with Adhesive Metal Treatment> In a preferred embodiment of the present invention, both the silver wire serving as the reference electrode 20 and the platinum wire serving as the working electrode 30 are embedded in the outer cylinder body 10 as the mating member. Prior to this, the surfaces of the electrodes 20 and 30 are preferably surface-treated with an adhesive primer (eg, an SH group-containing compound or a sulfur-containing compound).

In the present invention, in particular, when the surface treatment is performed by applying an adhesive metal treating agent containing the following triazine compound to the electrode surface, the electrode 2
Since the adhesiveness between the electrodes 20 and 30 and the cured body composed of the curable composition for electrode fixing (curable composition) for fixing 0 and 30 and the electrodes 20 and 30 can be improved, the working accuracy of the electrodes can be improved. preferable.

Examples of such an adhesive metal treating agent include 1,3,5-triazine-2,4-dithione derivatives containing a polymerizable double bond represented by the following formula (I) or (II): Among the 1,3,5-triazine-2,4-dithiol derivatives containing a polymerizable double bond represented by the formula (III) or (IV), those containing any triazine-based compound are preferably used.

[0076]

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[0077]

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[0078]

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[0079]

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(In the formulas (I) to (IV), n is 1 to 8, Y is oxygen or sulfur, R is an alkyl or allyl group having 1 to 8 carbon atoms, and Z is

[0081]

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One of the above). This metal surface treatment agent for adhesion contains a polymerizable double bond as described above,
3,5-triazine-2,4-dithione derivatives (I), (II)
Alternatively, 1,3,5-triazine-2,4-dithiol derivative (II
Since it contains (I) and (IV), the electrode surface that has been surface-treated with this treating agent exhibits excellent adhesion.

As such an adhesive metal surface treating agent, the compounds represented by the above formulas (I) to (IV) are used. Among them, 6- (4-vinylbenzyl-n-propyl) amino- 1,3,5-triazine-2,4-dithione, 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-
2,4-dithiol is preferred.

This 6- (4-vinylbenzyl-n-propyl)
Amino-1,3,5-triazine-2,4-dithione can be synthesized, for example, by the method described in JP-A-64-83254.

The metal surface treating agent for adhesion is prepared by using
(4-vinylbenzylpropyl) amino-1,3,5-triazine-2,4-dithione or 6- (4-vinylbenzylpropyl) amino-1,3,5-triazine-2,4-dithiol, for example Acetone, tetrahydrofuran, dioxane, acetonitrile, ethanol, N, N-dimethylformamide,
It is used by dissolving it in an organic solvent such as dimethyl sulfoxide at 0.1 to 10% by weight. When the dithione or dithiol is used by dissolving it in an organic solvent as described above, the surface of the electrodes 20, 30 can be easily subjected to an adhesive treatment by applying the dithione or dithiol to the surface of the electrode metal and then drying it as necessary.

Prior to applying the metal surface treating agent for bonding to the electrode surfaces, the surfaces of the electrodes (metals) 20 and 30 may be subjected to surface treatment such as sandblasting, heat oxidation, and electrolytic oxidation. it can.

In the present invention, it is preferable that after applying a surface treatment agent to the surface of the electrode metal, the surface of the electrode metal is immersed in an organic solvent such as acetone and subjected to ultrasonic cleaning. By doing so, the surplus monomer can be removed.

The electrode (metal) to be treated with such a bonding metal surface treatment agent is preferably a gold alloy, a gold-silver-palladium alloy, a silver alloy, or gold, palladium, platinum, silver, copper or the like. In the present invention, these electrodes having different ionization tendencies are used in an appropriate combination depending on the use or the like. For example, as an electrode for measuring oxygen content,
A silver (silver-silver chloride) reference electrode and a platinum working electrode, which are noble metal electrodes, are preferably used. When such a metal is subjected to surface treatment with the surface treatment agent, curing comprising the curable composition for electrode fixing (curable composition) containing the (meth) acrylic acid-based monomer and a polymerization initiator is performed. Shows excellent adhesion to the body. <Passing the electrode into the outer cylinder> Thus, the electrode (metal)
After each surface is treated with a surface treatment agent, these electrodes 20 and 30 are inserted into the outer cylinder 10. As the outer cylinder 10 used at this time, as shown in FIG.
Although it is possible to use one having no 0A, in order to reliably prevent electrical contact between the electrodes 20, 30 in the outer cylinder 10, an outer cylinder having a partition 10A as shown in FIG. Body 10 is preferred. In addition, such a partition body 10A
Is usually formed integrally with the outer cylinder 10 by extrusion molding or the like, but may be formed separately from the outer cylinder 10. When the partition body 10A is formed separately from the outer cylinder body 10 in this manner, for example, the electrodes 20 and 30 are fixed to the front and back surfaces of the partition body 10A so as to have a configuration shown in FIG. Preferably, the electrode is pasted with a curable composition, and the partition 10A with the electrodes 20, 30 is inserted into the outer cylinder 10 having no partition, as shown in FIG.

In the present invention, for example, two electrodes 2
The electrodes 20 and 30 are coated and fixed by disposing the electrodes 0 and 30 at a predetermined distance in a mold (not shown), pouring and curing the above-mentioned curable composition for electrode fixing (composition for electrode fixing). Then, by placing the obtained resin fixed electrode in a mold having the same diameter as the outer cylinder 10 and pouring the resin for forming the outer cylinder 10, the whole of the electrodes is further covered, and the outer cylinder with electrodes is formed. (The electrolyte crystal body 60 and the microporous membrane 80 before the formation in FIG. 2). The electrodes 20, 30
By arranging through the partition 10A, an outer cylinder with electrodes as shown in FIG. 1 (before forming the electrolyte crystal body 60 and the microporous membrane 80 in FIG. 1) is obtained. <Fixing of Electrode to Counterpart Member (Outer Cylindrical Body)> In the present invention, after the electrodes 20 and 30 are inserted into the outer cylindrical body 10 as described above, the electrode fixing composition is filled and cured. Outer cylinder 1
The electrodes 20 and 30 are fixed within zero. In particular, the partition 10
When the electrodes 20 and 30 are inserted into the outer cylinder 10 with A, the reference electrode 20 (eg, silver wire) is passed through one hole, and the working electrode 30 (eg, platinum wire) is passed through the other hole. Let it through.

In the present invention, the electrode-fixing composition is adhered to the surfaces of the electrodes 20 and 30, and before the composition is cured, the composition-adhered electrode is inserted into the outer cylinder 10.
The obtained electrode fixing composition may be further filled into the obtained outer cylindrical body 10 with electrodes 20 and 30 and cured. This is preferable because the composition can be easily filled and air bubbles hardly enter the composition. The electrode 2
0 and 30 without directly applying the electrode fixing composition to the electrode 2
When 0 and 30 are inserted and the uncured electrode-fixing composition is poured later, air bubbles may be mixed into the outer cylindrical body 10. Inclusion embedding may be insufficient. On the other hand, when the above method is used, the electrodes 20 and 30 can be completely buried, and air bubbles hardly enter the inside.

In order to fill the electrode fixing composition into the outer cylindrical body 10 through which the electrodes 20 and 30 are inserted, one end of the outer cylindrical body 10 through which the electrodes 20 and 30 are inserted is used. The composition may be inserted into the electrode fixing composition, and a suction pump may be arranged at the other end to suck the composition under reduced pressure.

As the electrode fixing composition, for example, a (meth) acrylic acid-based monomer, preferably an acidic group-containing monomer in an amount of 1 to 20% by weight is contained.
Acrylic acid-based monomers (a) and a polymerization initiator [example: tributylborane (TBB)] (b) are combined with (a) / (b) = 1 to 20 /
An electrode fixing composition as described above, which is contained in a volume ratio of 1 to 2, is used.

The filler obtained by reacting and curing such an electrode fixing composition preferably has a water absorption of as low as possible, usually 10% or less, more preferably 5% or less. If this water absorption is high, the electrode 2
A filler (eg, epoxy resin) such as an electrode fixing resin swells and covers the end surfaces 22 and 32 of the electrodes 0 and 30, and the characteristics of the ion measurement electrode 1 are changed. turn into.

After the electrode-fixing composition is filled in the outer cylinder 10 in this manner, the composition is cured by heating or at room temperature, whereby the resin is fixed as shown in FIG. 1 or FIG. Thus, an outer cylinder body with electrodes (before forming the electrolyte crystal body 60 and the microporous membrane 80 in FIGS. 1 and 2) is obtained. <Formation of Electrolyte Crystal and Microporous Membrane on End Face> In the present invention, one end face 50 of the electrode-equipped outer cylindrical body 10 fixed with resin as described above integrally covers the ends of these electrodes 20 and 30. Thus, the electrolyte crystal body 60 is formed.

As the electrolyte crystal body 60, a crystal made of an electrolyte, for example, a KCl crystal layer is formed in an electrode for measuring the amount of oxygen. In particular, in the case of a (noble metal) electrode for measuring the oxygen content, one end face 50 of the outer cylinder 10 is immersed in an electrolyte solution, for example, a KCl solution, before forming the electrolyte crystal body 60, and between the two electrodes. It is preferable to apply a voltage for a predetermined time to precipitate silver chloride on the surface of the reference electrode (silver electrode).

Next, a small amount (for example, 10
〜50 μl) of an electrolyte solution such as a KCl solution is dropped and evaporated to dryness to form a KCl crystal layer (electrolyte crystal 60), whereby the electrolyte crystal 60 is formed. The thickness of the electrolyte crystal body 60 is not particularly limited, but is usually 10 to
It is about 1000 μm. Note that a water-soluble polymer may be blended in the electrolyte solution such as the KCl solution,
When such a water-soluble polymer is blended, it is uniform,
The electrolyte crystal body 60 such as a fine KCl crystal layer is
2, 32 are preferable.

Next, these electrodes 20 and 30, the cured products 40A and 40B of the electrode fixing composition and the electrolyte crystal (K
A microporous film 80 integrally covering the outer peripheral region 70 at one end of the Cl crystal layer 60 is formed on the surface thereof to prevent elution (outflow) to the outside of the electrolyte crystal body 60 while securing electrical conductivity. In the present invention, instead of the microporous membrane, a membrane having electrical conductivity and an ability to prevent elution of the electrolyte crystal body 60, more preferably having a low water absorption rate, and excellent in safety and the like (eg:
As long as it is a conductive film, a film that does not necessarily have micropores can be used.

In order to form such a microporous film 80 on the surface 70 of the electrolyte crystal (eg, KCl crystal) 60, for example, an electrode on which the electrolyte crystal (electrolyte crystal layer) is formed is formed by using a polyurethane solution or the like. After dipping in a resin solution of the above, it is lifted up and left standing at normal temperature and under heating to form a microporous film 80 of polyurethane or the like on the electrode surface (immersion method, dipping method). When the thickness of the polyurethane film formed by one immersion is small, the film thickness can be easily adjusted by repeating immersion-drying a plurality of times. According to such an immersion method, the resulting microporous membrane 80 (polyurethane membrane) has a smooth junction with the outer cylinder 10 in the outer peripheral region 70.

The microporous membrane 80 thus obtained has a thickness of usually 10 to 1000 μm, preferably 50 to 200 μm.
It is about μm. The material of the microporous membrane 80 is not particularly limited as long as it has the above-described functions, and specific examples include polyurethane, polyvinyl chloride, polystyrene, polyethylene, polypropylene, polycarbonate, and ethyl cellulose. Can be In the present invention, it is preferable to be formed of the same material as the outer cylinder 10, for example, polyurethane, in terms of adhesion between the outer cylinder 10 and the microporous membrane 80, durability, and the like.

The ion measuring electrode thus obtained, particularly the oxygen electrode, is flexible, has a low water absorption, and can be used for a long period of time (1 to 4) with good reproducibility regardless of the use site. 3 weeks). Also, the electrode is
It has excellent impact resistance and safety, and can be used by inserting it into human blood vessels.

In such an ion measuring electrode 1, particularly an oxygen electrode, oxygen molecules (oxygen partial pressure) that have moved from outside the microporous membrane (polyurethane membrane) 80, such as into a blood vessel, through the microporous membrane (polyurethane membrane) 80. The amount is being measured. In the oxygen electrode 1, water that has permeated into the microporous membrane (polyurethane membrane) 80 from the outside at the time of measuring the amount of oxygen and has penetrated into the portion where the electrolyte crystal (KCl crystal) 60 is present is used. The KCl crystal 60 is dissolved to form an electrolyte (saturated) solution, and the polyurethane film 80 swells outward with the generation of the electrolyte solution. In such a state, it is considered that the following reaction occurs on the end faces 22, 32 of the oxygen electrodes 20, 30. For example, when the reference electrode (anode) 20 is formed of silver (Ag) (Ag-AgCl), (1) Ag → Ag ⁺⁺ on the side of the anode 20
e ⁻ , (2) Ag ⁺ + Cl ⁻ occurs, and the working electrode (cathode) 30 is formed of platinum (Pt).
On the cathode side, (1) O ₂ + 2H ₂ O + 2e ⁻ → H ₂ O ₂ +2
_{^{OH -, (2) 2H 2}} O 2 + 2e - believed to become reaction occurs ^- → 2OH.

In the ion measuring electrode 1 of the present invention,
In the case of measuring other molecules (ions), the ion measuring electrode 1 may be used in combination with an oxygen reaction or the like as appropriate, for example, by generating oxygen molecules when a certain substance is decomposed by oxygen. It can also be applied to the measurement of molecules (ions).

When the oxygen content (oxygen partial pressure) is measured as described above, the microporous membrane (polyurethane membrane) 80 and the electrode end 2
Water penetrates or penetrates into the [portion where the electrolyte crystal (KCl crystal) 60 is present] between the electrodes 2 and 32, and the water is in contact with the electrode-fixing composition cured product 40 (40A, 40B) for a long time (eg, 1).
The cured body 40 (40A, 40B) even when contacted
Does not swell, and therefore does not cover the electrode ends 22, 32. For example, even when used as an indwelling type sensor, the measurement accuracy of the oxygen (partial pressure) amount hardly decreases. .

[0104]

According to the present invention, the water absorption is low, and accurate measurement of the oxygen content and the like can be performed with good reproducibility regardless of the use site.
An electrode fixing composition that can easily form a bendable electrode can be provided. Further, according to the method for fixing an electrode according to the present invention, the composition such as a noble metal electrode can be easily fixed by filling and applying the composition between the electrode and a counterpart member such as a tube.

The ion sensor (electrode for measuring ions), particularly the oxygen electrode, according to the present invention has a low water absorption and can measure the amount of oxygen in a place with a large amount of water. Accurate measurement of the amount of oxygen and the like can be performed, and the sensor is flexible. Such an electrode (ion sensor) can be easily manufactured.

Further, according to the present invention, an electrode such as a noble metal electrode is easily fixed to a tube or the like without requiring a special technique, and the moisture in the measurement environment is not affected by the site where the electrode is used, such as in a blood vessel. Provided is an oxygen electrode that can be used without being affected by the oxygen.

[0107]

The curable composition for fixing an electrode, the method for fixing an electrode, a noble metal electrode, and an electrode for measuring the amount of oxygen (oxygen electrode) according to the present invention will be described more specifically below. The examples are not to be construed as limiting in any way.

[0108]

EXAMPLE 1 A platinum wire having an outer diameter of 25 .mu.m and a silver wire having a diameter of 250 .mu.m were each treated with 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol at 5% by weight.
The surface was treated with a dissolved acetone solution (“V primer”, manufactured by Sun Medical Co., Ltd.) and dried.

On the other hand, 4-methacryloyloxyethyl trimellitic acid methacrylate anhydride [4-META] was 5% by weight, 4,4′-bis (4-methacryloyloxyethylphenol) propane was 10% by weight, and 2-hydroxyethyl A glass plate was prepared by dissolving 35% by weight of methacrylate and 50% by weight of methyl methacrylate (total 100% by weight) (a) and tributylborane (“TBB”, manufactured by Sun Medical Co., Ltd.) (b). And mixed at a volume ratio ((a) :( b)) = 3: 1.

Next, the resulting mixture was adhered to the surface-treated platinum wire having an outer diameter of 25 μm and the surface-treated silver wire having an outer diameter of 250 μm on a glass plate. And before this admixture hardens, the inside is divided into two parts with a diameter of 1 mm
A platinum wire treated with the admixture was passed through one hole of the polyurethane tube, and a silver wire treated with the admixture was passed through the other hole.

After the mixture on the surface of the platinum wire and the silver wire (both are also referred to as electrodes) is cured, the mixture is sucked and filled into the polyurethane tube through which the electrodes are passed by using a pump. Then, the gap in the tube was filled.
After filling the mixture, the mixture was allowed to stand for 8 hours, and then the tip of the obtained electrode-embedded tube was cut.

Then, the cut portion of the electrode-embedded tube was immersed in a KCl solution, and a voltage of 3 volts was applied between the two electrodes for 5 minutes to deposit silver chloride on the surface of a silver electrode serving as a reference electrode. Next, 20 μl of a KCl solution was dropped on these electrode surfaces and evaporated to dryness to form a KCl crystal layer.

The electrode on which the crystal layer was formed was dipped in a polyurethane solution, pulled up, and left overnight to form a polyurethane film on the electrode surface.

[0114]

Example 2 A platinum wire having an outer diameter of 25 μm and a silver wire having a diameter of 250 μm were each converted to 6% by weight of 6- (4-vinylbenzyl-n-propyl) amino-1,3,5-triazine-2,4-dithiol. The surface was treated with an acetone solution (“V Primer”, manufactured by Sun Medical Co., Ltd.) dissolved in the amount described above and dried.

On the other hand, 4-methacryloyloxyethyl trimellitate methacrylate anhydride [4-META] is 5% by weight, 4,4′-bis (4-methacryloyloxyethylphenol) propane is 10% by weight, and 2-hydroxyethyl A solution prepared by dissolving 35% by weight of methacrylate and 50% by weight of methyl methacrylate (1% in total)
00% by weight) (a) and tributylborane (“TBB”,
And (b) from Sun Medical Co., Ltd.
The mixture was mixed at a volume ratio ((a) :( b)) = 3: 1.

Next, on the glass plate, the mixture obtained as described above was respectively attached to the above-mentioned surface-treated platinum wire having an outer diameter of 25 μm and the above-mentioned surface-treated silver wire having an outer diameter of 250 μm.

Before the admixture is cured, the adsorbent-adhered platinum wire is passed through one hole of a polyurethane tube having a diameter of 1 mm, the inside of which is divided into two parts, and the adsorbate adhering is passed through the other hole. The treated silver wire was passed.

After the mixture on the surface of the platinum wire and the silver wire (both are also referred to as electrodes) is cured, epoxy resin is suctioned and filled into the polyurethane tube through which the electrodes are passed by using a pump. The gap in the tube was filled.

After filling the epoxy resin and leaving it for 8 hours,
The tip of the obtained electrode-embedded tube was cut. Next, the cut portion of the electrode-embedded tube was immersed in a KCl solution, and a voltage of 3 volts was applied between both electrodes for 5 minutes to deposit silver chloride on the surface of a silver electrode serving as a reference electrode.

Next, 20 μl of KC was placed on the surface of these electrodes.
1 solution was added dropwise and evaporated to dryness to form a KCl crystal layer. The electrode on which the crystal layer was formed was immersed in a polyurethane solution, pulled up, and left overnight to form a polyurethane film on the electrode surface.

[0121]

[Reference Example 1] A platinum wire with an outer diameter of 25 µm was passed through one hole of a polyurethane tube having a diameter of 1 mm and the inside of which was divided into two parts, and the same process was applied to the other hole.
m of silver wire.

On the other hand, on a glass plate, an epoxy resin (“2001”, manufactured by Three Bond Co.) as a main agent and “2” as a curing agent were used.
105C "(manufactured by Three Bond Co., Ltd.)
The mixture was mixed at a ratio of 00:50 (weight ratio). Before the obtained mixture was cured, the mixture was sucked and filled into the polyurethane tube through which the electrode was passed by using a pump.

After the mixture was filled, the tube was allowed to stand for 24 hours, and then the tip of the tube was cut. Next, the cut portion of the tube was immersed in a KCl solution, and a voltage of 3 volts was applied between both electrodes for 5 minutes to deposit silver chloride on the surface of a silver electrode serving as a reference electrode.

Next, 20 μl of KC was applied to the surface of these electrodes.
1 solution was evaporated and evaporated to dryness to form a KCl crystal layer. The electrode on which the crystal layer was formed was immersed in a polyurethane solution, pulled up, and left overnight to form a polyurethane film on the electrode surface.

A constant voltage of 0.8 V was applied to the electrodes prepared in Examples 1 and 2 and the electrodes were immersed in water saturated with air for 7 days, and the current between the electrodes was measured. It was 5% or less as compared with immediately after.

Further, in the electrode manufactured in Reference Example 1, the change in the current value was 30% or more, and it was not practically possible to measure the amount of oxygen ions and the like. By fixing the noble metal electrode using a composition containing a methacrylic acid-based monomer and a tributylborane catalyst,
The electrode itself has flexibility, and it is possible to easily produce an oxygen electrode capable of practically performing measurement even in the presence of water.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram showing a preferred embodiment of an ion measuring electrode (ion sensor) according to the present invention having a partition wall, and FIG. 1 (a) is shown in FIG. 1 (b). FIG. 3 is a cross-sectional view of the ion measurement electrode taken along line AA. FIG. 1 (b)
FIG. 2 is a longitudinal sectional view of the ion measurement electrode shown in FIG.

FIG. 2 is a conceptual diagram showing a preferred embodiment of an ion measurement electrode (ion sensor) according to the present invention having no partition wall, and FIG. 2 (a) is shown in FIG. 2 (b). It is a longitudinal cross-sectional view of the electrode for ion measurement. FIG. 2 (a) is a diagram corresponding to B in FIG. 2 (b).
FIG. 3 is a cross-sectional view taken in the direction of arrow B.

[Explanation of symbols]

 1 ... Ion measurement electrode 10 ... Outer cylinder (counterpart) 10A ... Partition wall 20 ... Reference electrode 22, 32 ... Electrode end face 30 ... Action Electrodes 40, 40A, 40B... Cured body of electrode fixing composition 50... One end surface of outer cylinder 60... Electrolyte crystal 70. .... Microporous membranes

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor: Nobuyoshi Tanaka 52, Minamihango, Yamagata City, Yamagata Prefecture (72) Inventor: Nobuo Nakabayashi 5-6-20 Koganehara, Matsudo City, Chiba Prefecture (72) Inventor: Stone Kazuhiko Hara 3-16-37, Josuihonmachi, Kodaira-shi, Tokyo (72) Inventor Tetsuya Toida 571-2 Furutakacho, Moriyama-shi, Shiga Prefecture Inside Sun Medical Co., Ltd.

Claims (7)

[Claims] 1. A method comprising the steps of: (1) containing a (meth) acrylic acid monomer; and 0.1 to 30 parts by weight of a polymerization initiator based on 100 parts by weight of the (meth) acrylic acid monomer. Curable composition for fixing electrodes. 2. The method according to claim 1, wherein the (meth) acrylic acid-based monomer is
The curable composition for fixing an electrode according to claim 1, wherein the curable composition for fixing an electrode contains an acidic group-containing monomer in an amount of 1 to 20% by weight. 3. The method according to claim 1, wherein when the electrode surface-treated with the adhesive metal treating agent is fixed to a counterpart member, the composition according to claim 1 is filled between the electrode and the counterpart member. A method for fixing an electrode, comprising: 4. The method according to claim 1, wherein the adhesive metal treating agent contains a polymerizable double bond represented by the following formula (I) or (II).
Triazine-2,4-dithione derivative, any one of 1,3,5-triazine-2,4-dithiol derivatives containing a polymerizable double bond represented by the following formula (III) or (IV) The method according to claim 3, which is an adhesive metal treating agent containing a system compound. Embedded image Embedded image Embedded image (In the formulas (I) to (IV), n is 1 to 8, Y is oxygen or sulfur, R is an alkyl group or an allyl group having 1 to 8 carbon atoms, and Z is One of the above). 5. An outer cylindrical body made of a flexible resin formed in a substantially cylindrical shape, and a reference electrode and a function arranged apart from each other in the outer cylindrical body along a longitudinal direction of the outer cylindrical body. Electrodes, a cured product of the electrode fixing composition filled between the electrodes and the outer cylinder, and fixed to one end surface of the outer cylinder so as to integrally cover the ends of these electrodes. An electrode for ion measurement, comprising: an electrolyte crystal; and a microporous film that integrally covers the electrode, a cured product of the electrode fixing composition, and an outer peripheral area of one end of the electrolyte crystal. 6. An outer cylinder made of a flexible resin formed in a substantially cylindrical shape, and silver-silver chloride made of silver-silver chloride disposed in the outer cylinder along the longitudinal direction of the outer cylinder. A reference electrode and a working electrode made of platinum, a cured body of the electrode fixing composition filled between these electrodes and the outer cylinder, and one end face of the outer cylinder, the ends of these electrodes are integrally formed. An electrolyte crystal made of KCl crystal fixed so as to cover the electrode, a cured body of the electrode, the electrode fixing composition, and a microporous membrane integrally covering one end outer peripheral area of the electrolyte crystal; An oxygen electrode, wherein the cured product of the composition for use is obtained by reacting and curing a composition containing a (meth) acrylic acid-based monomer and a polymerization initiator. 7. The reference electrode and the working electrode are surface-treated with an adhesive metal treating agent containing a triazine compound of any of the above formulas (I) to (IV). The electrode according to any one of claims 5 to 6.