JPH08136446A - Analytical cell made out of resin in cyclic olefin system - Google Patents

Abstract

PURPOSE: To provide the analytical cell which is excellent in a light transmission factor, in a light transmission factor in the ultraviolet ray area in particular, and also excellent in chemical resistance by forming the analytical cell out of specified resin in a cyclic olefin system. CONSTITUTION: As resin in a cyclic olefin system, at least one kind selected out of graft denatured products of polymers such as random copolymer of ethylene with cyclic olefin, ring opening polymer in a cyclic olefin system, and hydride of ring opening polymer, namely one out of these polymers is used by itself, or polymer combined with one another is used. Out of them, cyclic olefin random copolymer is preferably used. Resin in a cyclic olefin system is formed into a desired shape and size by means of a molding method appropriately selected out of injection molding, blow molding and the like, so that the analytical cell is thereby manufactured. The aforesaid analytical cell is excellent in a light transmission factor, in a light transmission factor in the ultraviolet ray area in particular, and also excellent in chemical resistance. Therefore, the analytical cell can be utilized as a replacement of a former glass made analytical cell.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an analytical cell, and more particularly to an analytical cell formed from a cyclic olefin resin having excellent light transmittance, particularly in the ultraviolet region, and excellent chemical resistance.

[0002]

BACKGROUND OF THE INVENTION Analytical cells used in ultraviolet spectroscopic analyzers and the like are required to have excellent light transmittance, particularly light transmittance in the ultraviolet region as well as chemical resistance. For this reason, glass has been conventionally used as the material for the analysis cell. In recent years, as a material for this analysis cell, replacement of glass with a transparent resin, which has a low specific gravity and is easy to discard, has been studied.

Examples of conventionally known transparent resins capable of forming such an analysis cell include polycarbonate, polystyrene, polyvinyl chloride, polymethylmethacrylate, etc., and all of these resins have a light transmittance, particularly in the ultraviolet region. The light transmittance of the
There is a problem of poor resistance to alkalis.
For this reason, it has been desired to develop a transparent resin analysis cell which has excellent light transmittance, particularly in the ultraviolet region, and also excellent chemical resistance, and which can replace the glass analysis cell.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is formed from a cyclic olefin resin having excellent light transmittance, particularly in the ultraviolet region, and excellent chemical resistance. The purpose is to provide a calibrated analysis cell.

[0005]

SUMMARY OF THE INVENTION An analysis cell comprising a cyclic olefin resin according to the present invention has the following [A-1], [A-2], [A-3] and
It is characterized by being formed from at least one cyclic olefin resin selected from [A-4].

[A-1] Ethylene and the following formula [I] or [I
I] an ethylene / cyclic olefin random copolymer obtained by copolymerizing with a cyclic olefin;

[0007]

Embedded image

(In the formula [I], n is 0 or 1, and m is
Is 0 or a positive integer, q is 0 or 1, and R
^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group which may be substituted with a halogen, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. May be. ),

[0009]

[Chemical 4]

(In the formula [II], p and q are 0 or a positive integer, m and n are 0, 1 or 2, and R ¹
To R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may be substituted with a halogen or an alkoxy group, wherein the carbon atom to which R ⁹ or R ¹⁰ is bonded and R ¹³ are bonded to each other. To the carbon atom to which R ¹¹ is bonded or directly to the carbon atom to which R ¹¹ is bonded through an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ^{12 15} and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. ), [A-
2] A ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [A-3] a hydride of the above ring-opening polymer or copolymer [A-2], And [A-4] Above [A-
1], [A-2] or [A-3] graft modified product.

In the present invention, the above cyclic olefin resin is an ethylene / cyclic olefin random copolymer [A-1].
It is preferred that

[0012]

DETAILED DESCRIPTION OF THE INVENTION The analysis cell according to the present invention is formed of a specific cyclic olefin resin. Hereinafter, the cyclic olefin resin forming the analysis cell according to the present invention will be described first.

In the present invention, as the cyclic olefin resin, a random copolymer of [A-1] ethylene and a cyclic olefin represented by the following formula [I] or [II], [A-2]
A ring-opening polymer or copolymer of a cyclic olefin represented by the following formula [I] or [II], [A-3] a hydrogenated product of the above [A-2] ring-opening polymer or copolymer, and [ A-4] Above [A
-1], [A-2] or at least one selected from the graft modified products of [A-3].

The softening temperature (TMA) of the cyclic olefin resin used in the present invention measured by a thermal mechanical analyzer is 0 ° C. or higher, preferably 10 to 200 ° C.
More preferably, it is 10 to 180 ° C., and the glass transition point (Tg) is −10 ° C. to 190 ° C., preferably 0 to 170.
It is desirable that the temperature is ° C.

The crystallinity of the cycloolefin resin used in the present invention is 0 to 20 as measured by the X-ray diffraction method.
%, Preferably 0 to 2%. The intrinsic viscosity [η] of the cyclic olefin-based resin measured in decalin at 135 ° C. is 0.05 to 10 dl / g, and preferably 0.0 to 10 dl / g.
3-2.0 dl / g, more preferably 0.4-1.2 dl / g
It is desirable that

First, the cyclic olefin cyclic olefin represented by the formula [I] or [II] which forms the cyclic olefin resin used in the present invention will be described. Cyclic olefin

[0017]

Embedded image

In the above formula [I], n is 0 or 1,
m is 0 or a positive integer, and q is 0 or 1.
When q is 1, R ^a and R ^b are each independently the following atoms or hydrocarbon groups, and when q is 0, each bond is bonded to form a 5-membered ring. Form.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

As the hydrocarbon group, an alkyl group usually having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group can be mentioned each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group, and a cycloalkyl group. Examples thereof include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

These hydrocarbon groups may be substituted with a halogen atom. Further, in the above formula [I], R
^{15 to} R ¹⁸ may be bonded to each other (cooperatively with each other) to form a monocycle or polycycle, and the monocycle or polycycle thus formed has a double bond. Good. The monocyclic or polycyclic rings formed here are specifically exemplified below.

[0022]

[Chemical 6]

In the above exemplification, the carbon atoms numbered 1 or 2 are each R in the formula [I].
Represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

[0024]

[Chemical 7]

In the formula [II], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. Also R
^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom,
It is a hydrocarbon group or an alkoxy group.

The halogen atom has the same meaning as the halogen atom in the above formula [I]. Further, as the hydrocarbon group, an alkyl group having 1 to 20 carbon atoms,
Examples thereof include halogenated alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, as the alkyl group,
Examples include methyl group, ethyl group, propyl group, isopropyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group and octadecyl group, and cycloalkyl groups include cyclohexyl group and aromatic hydrocarbon group. Examples thereof include an aryl group and an aralkyl group, specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group, a phenylethyl group and the like.

Examples of the alkoxy group include methoxy group, ethoxy group and propoxy group.
These hydrocarbon group and alkoxy group may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or with 1 to 10 carbon atoms.
It may be bonded via the alkylene group of 3. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ or the groups represented by R ¹⁰ and R ¹¹ cooperate with each other, It forms an alkylene group of any one of a methylene group (-CH _2- ), an ethylene group (-CH ₂ CH _2- ) or a propylene group (-CH ₂ CH ₂ CH _2- ).

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, as the monocyclic or polycyclic aromatic ring, for example, n = m = 0 as shown below.
In this case, a group in which R ¹⁵ and R ¹² further form an aromatic ring can be mentioned.

[0030]

Embedded image

Here, q has the same meaning as q in the formula [II]. Specific examples of the cyclic olefin represented by the above formula [I] or [II] are shown below.

[0032]

[Chemical 9]

(In the above formula, the numbers 1 to 7 represent the position number of carbon.) And a derivative obtained by substituting the bicyclo [2.2.1] -2-heptene with a hydrocarbon group. Examples of this hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl and 5-methyl-5. -Phenyl, 5-benzyl, 5
-Tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α
-Naphthyl), 5- (anthracenyl), 5,6-diphenyl and the like.

As other derivatives, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-
Tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a
-Bicyclo [2.2.1] such as hexahydroanthracene-
Examples include 2-heptene derivatives.

Tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-
Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives such as methyltricyclo [4.3.0.1 ^2,5 ] -3-decene and 5-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, Tricyclo [4.4.0.1
^2,5 ] -3-Undecene, 10-methyltricyclo [4.4.0.1
^2,5 ] -3-Undecene and other tricyclo [4.4.0.1 ^2,5 ] -3
-Undecene derivative.

[0036]

[Chemical 10]

(In the above formula, the numbers 1 to 12 represent the position number of carbon) and derivatives thereof in which a hydrocarbon group is substituted. Examples of this hydrocarbon group include 8-methyl,
8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-
Hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10-dimethyl, 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-Dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl, 9,11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-1
1,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9-methyl, 8-ethylidene-9-ethyl,
8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8
-n-propylidene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9- Ethyl, 8-isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl
-8-phenyl, 8-benzyl, 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- ( α-naphthyl), 8- (anthracenyl), 5,6-diphenyl and the like.

Still another derivative is an adduct of (cyclopentadiene-acenaphthylene adduct) with cyclopentadiene. Pentacyclo [6.5.1.1
^3,6. 0 ^2,7 .0 ^9,13 ] -4-Pentadecene and its derivatives.

[0039] pentacyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13]
-3-Pentadecene and its derivatives. Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4,10- penta octadecadienoic Penta cyclopentadiene octadecadienoic compound such.

[0040] pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13]
-3-Hexadecene and its derivatives. Pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene, and derivatives thereof.

[0041] hexacyclo [6.6.1.1 ^3,6 .1 ^10,13 .0 ^2,7 .0
^9,14] -4-heptadecene and derivatives thereof. Heptacyclo ^{[8.7.0.1 2,9 .1 4,7 .1 11,17 .0} 3,8 .0 12,16] -5- eicosene, and derivatives thereof.

[0042] heptacyclo [8.8.0.1 ^2,9 .1 ^4,7 .1 ^11,18 .0
^3,8 .0 ^12,17] -5-heneicosene, and a derivative thereof.
Octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0
^12,17 ] -5-Dococene and its derivatives.

[0043] Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1 ^15,18.
0 ^2,10 .0 ^3,8 .0 ^12,21 .0 ^14,19] -5-pentacosene and derivatives thereof. Nonashikuro [10.10.1.1 ^5,8 .1 ^14,21.
1 ^{16, 19} .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^{15, 20]} -6-hexacosenoic,
And derivatives thereof.

Although specific examples of the cyclic olefin represented by the general formula [I] or [II] are shown above, more specific structural examples of these compounds are described in Japanese Patent Application No. Hei. -196475, paragraph number [003
The structural examples of the cyclic olefins shown in 2] to [0054] can be used.

The cyclic olefin represented by the above general formula [I] or [II] can be produced by subjecting cyclopentadiene and olefins having a corresponding structure to a Diels-Alder reaction.

These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin resin used in the present invention can be prepared by using the cyclic olefin represented by the formula [I] or [II] as described above, for example, in JP-A-60-168708, JP-A-61-120816 and JP-A-61-120816.
-115912, 61-115916, 61-271308, 61-2722
Nos. 16, 62-252406, 62-252407, etc., according to the method proposed by the present applicant, and by appropriately selecting conditions, it can be produced.

[A-1] Ethylene / Cyclic Olefin Random
The copolymer [A-1] ethylene / cyclic olefin random copolymer usually has a constitutional unit derived from ethylene from 30 to 9
It contains structural units derived from cyclic olefins in an amount of 0 mol%, preferably 40 to 85 mol%, usually 10 to 70 mol%, preferably 15 to 60 mol%. The ethylene composition and cyclic olefin composition are ¹³
Measured by C-NMR. In this [A-1] ethylene / cyclic olefin random copolymer, the structural units derived from ethylene and the structural units derived from cyclic olefin as described above are randomly arranged and bonded, It has a linear structure. The fact that this copolymer is substantially linear and does not have a substantially gel-like crosslinked structure means that when this copolymer is dissolved in an organic solvent, this solution contains insoluble components. Can be confirmed by not. For example, when measuring the intrinsic viscosity [η], it can be confirmed by completely dissolving this copolymer in decalin at 135 ° C.

In the [A-1] ethylene / cyclic olefin random copolymer used in the present invention, the above formula [I]
Alternatively, at least a part of the cyclic olefin represented by [II] is considered to constitute the repeating unit represented by the following formula [III] or [IV].

[0049]

[Chemical 11]

In the formula [III], n, m, q, R ¹ to
R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0051]

[Chemical 12]

In the formula [IV], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Further, the [A-1] ethylene / cycloolefin random copolymer used in the present invention has a structural unit derived from another copolymerizable monomer, if necessary, within a range not impairing the object of the present invention. May be.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefins, and specific examples include propylene, 1-butene, 1-pentene, 1-hexene and 3-. Methyl-1-butene, 3-
Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-
Α- with 3 to 20 carbon atoms such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene
Olefin, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano -1 H-indene and other cycloolefins, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2 -Non-conjugated dienes such as norbornene can be mentioned.

These other monomers can be used alone or in combination. [A-1] Ethylene
In the cyclic olefin random copolymer, the constitutional unit derived from the other monomer as described above is usually 20
It may be contained in an amount of not more than mol%, preferably not more than 10 mol%.

The [A-1] ethylene / cyclic olefin random copolymer used in the present invention comprises ethylene and a compound of the formula [I].
Alternatively, it can be produced by the production method disclosed in the above publication using a cyclic olefin represented by [II]. Among these, this copolymerization is carried out in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst for [A-1] ethylene / cyclic olefin random copolymerization. It is preferred to produce a polymer.

In this copolymerization reaction, a solid group IVB metallocene catalyst can also be used. Where solid IV
The Group B metallocene catalyst is a catalyst composed of a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound to be blended if necessary. Here, the group VI transition metal is zirconium, titanium or hafnium, and these transition metals have at least one ligand having a cyclopentadienyl skeleton. here,
Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group which may be substituted with an alkyl group, an indenyl group, a tetrahydroindenyl group and a fluorenyl group. These groups may be bonded via another group such as an alkylene group. Further, ligands other than the ligand having a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like.

Further, as the organoaluminum oxy compound and the organoaluminum compound, those generally used for the production of olefin resins can be used. Such a solid group IVB metallocene catalyst is described in, for example, JP-A-61-221206, JP-A-64-106, and JP-A-2-173112.

[A-2] Ring-Opening Polymer of Cyclic Olefin or
In the ring-opening polymer or ring-opening copolymer of the copolymer cyclic olefin, at least a part of the cyclic olefin represented by the above formula [I] or [II] is represented by the following formula [V] or [VI]. It is considered that they constitute the repeating unit.

[0059]

[Chemical 13]

In the formula [V], n, m, q and R ¹
R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0061]

Embedded image

In the formula [VI], n, m, p, q and R ^{1 to} R ¹⁹ have the same meanings as in the formula [II]. Such a ring-opening polymer or a ring-opening copolymer can be produced by the production method disclosed in the above-mentioned gazette. It can be produced by polymerization or copolymerization below.

As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound and a reducing agent, or titanium, A catalyst composed of a halide of a metal selected from palladium, zirconium, molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

[A-3] Hydrogenation of Ring-Opening Polymer or Copolymer
The hydride of the ring-opening polymer or copolymer [A-3] used in the present invention is obtained by converting the ring-opening polymer or copolymer [A-2] obtained as described above into a conventionally known hydrogen-containing compound. It is obtained by hydrogenation in the presence of an added catalyst.

In the hydride of the [A-3] ring-opening polymer or copolymer, at least a part of the cyclic olefin represented by the formula [I] or [II] is represented by the following formula [VII]
Alternatively, it is considered to have a repeating unit represented by [VIII].

[0066]

[Chemical 15]

In the formula [VII], n, m, q and R
^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as in formula [I].

[0068]

Embedded image

In the formula [VIII], n, m, p, q, R
^{1 to} R ¹⁹ have the same meaning as in formula [II]. [A-4] Graft-modified product The graft-modified product of the cyclic olefin resin is the same as the above [A-
1] Ethylene / Cyclic Olefin Random Copolymer, [A-
2] A ring-opening polymer or copolymer of a cyclic olefin, or a graft-modified product of a hydride of the [A-3] ring-opening polymer or copolymer.

As the modifier, unsaturated carboxylic acids are usually used, and specifically, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, Unsaturated carboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydrides and unsaturated Examples thereof include carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids.

Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Among these modifiers, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic acid anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. These modifiers can be used in combination of two or more.

The modification ratio of the graft modified product of the cyclic olefin resin used in the present invention is usually preferably 10 mol% or less. Such a graft modified product of a cyclic olefin-based resin can be produced by blending a cyclic olefin-based resin with a modifying agent so as to have a desired modification ratio and then graft-polymerized. It can also be produced by preparing and then mixing this modified product with an unmodified cyclic olefin resin.

In order to obtain a graft modified product of a cyclic olefin resin from a cyclic olefin resin and a modifier, conventionally known polymer modification methods can be widely applied.
For example, a graft-modified product is obtained by a method of adding a modifier to a molten cyclic olefin-based resin and performing graft polymerization (reaction), or a method of adding a modifier to a solvent solution of the cyclic olefin-based resin and performing a graft reaction. be able to.

Such a graft reaction is usually carried out at 60 to 3
It is carried out at a temperature of 50 ° C. The graft reaction can be carried out in the presence of a radical initiator such as an organic peroxide and an azo compound.

A modified product having a modification ratio as described above can be obtained directly by a graft reaction between a cyclic olefin resin and a modifying agent, and a high modification ratio can be obtained in advance by a graft reaction between the cyclic olefin resin and a modifying agent. It is also possible to obtain the modified product by diluting the modified product with an unmodified cyclic olefin resin so as to obtain a desired modification ratio.

In the present invention, as the cyclic olefin resin, the above-mentioned [A-1], [A-2], [A-3] and [A-3] are used.
-4] can be used alone or in combination.

Of these, ethylene / cyclic olefin random copolymer [A-1] is preferably used. In the present invention, the layer formed from the cyclic olefin resin as described above may contain other components within a range that does not impair the object of the present invention, for example, additives, other transparent resins, impact. Rubber component to improve strength (EPR, E
PDM, SBS, SEBS, etc.).

In the present invention, in order to manufacture an analytical cell from the above cyclic olefin resin, a method such as an injection molding method or a blow molding method is appropriately selected and molded into a desired shape and size. You can

The shape of the analysis cell made of the cyclic olefin resin according to the present invention is not particularly limited. In addition, the non-light-transmitting side surface of the analysis cell formed in a rectangular tube shape may be surface-embossed.

In the analysis cell composed of the cyclic olefin resin according to the present invention, the thickness (resin) is not particularly limited, but is 0.1 to 10 mm, preferably 0.5 to 5 mm.
It is desirable that

[0082]

The analysis cell comprising the cyclic olefin resin according to the present invention is excellent in light transmittance, particularly in the ultraviolet region, and has excellent chemical resistance. Can be used as

[0083]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0084]

Example 1 MFR (at 260 ° C. and 2.16 kg condition)
Is 30 g / 10 min, the intrinsic viscosity [η] (in decalin at 135 ° C.) is 0.60 dl / g, and the TMA (measured by a thermal mechanical analyzer) is 90 ° C. ethylene and tetracyclo [4.4.0.1 ^{2, 5.1 7,10]} -3-random copolymer of dodecene (hereinafter referred ETCD-3) by injection molding, 10 × 10 × 40mm, to form the analysis cell of the resin thickness 1 mm.

300 n from the lateral direction of the obtained analysis cell
m, 340 nm and 400 nm light rays were applied, and the light transmittance of these wavelengths was measured. The results are shown in Table 1. Further, a chemical resistance test was conducted on this analytical cell.

The chemical resistance was evaluated by the appearance after immersing the analytical cell in the chemicals shown in Table 2 for 1 month at room temperature. Table 2 shows the results.

[0087]

[Comparative Examples 1 to 4] Instead of ETCD-3, polystyrene (PS), polycarbonate (PC), vinyl chloride (P
VC) and polymethylmethacrylate (PMMA) were used respectively, and an analysis cell was obtained in the same manner as in Example 1.

The results of measuring the light transmittance of each analysis cell in the same manner as in Example 1 are shown in Table 1. Table 2 shows the results of the chemical resistance test conducted in the same manner as in Example 1.

[0089]

[Table 1]

[0090]

[Table 2]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08G 61/08 NLG

Claims (2)

[Claims] 1. The following [A-1], [A-2], [A-3] and [A-
4] An analysis cell made of a cyclic olefin-based resin, characterized by being formed from at least one cyclic olefin-based resin selected from [A-1] ethylene and represented by the following formula [I] or [II]: Ethylene / cyclic olefin random copolymer obtained by copolymerization with a cyclic olefin (In the formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently hydrogen. Atom, a halogen atom or a hydrocarbon group optionally substituted with halogen, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic ring or a polycyclic ring, and the monocyclic ring or the polycyclic ring is It may have a double bond, and is R ¹⁵ and R ¹⁶ , or R
¹⁷ and R ¹⁸ may form an alkylidene group. ), [Chemical formula 2] (In the formula [II], p and q are 0 or a positive integer,
m and n are 0, 1 or 2, R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group optionally substituted with a halogen or an alkoxy group,
The carbon atom to which R ⁹ or R ¹⁰ is bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are bonded directly or through an alkylene group having 1 to 3 carbon atoms. Or when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. ), [A-2] ring-opening polymer or copolymer of the cyclic olefin represented by the above formula [I] or [II], [A-3] the above ring-opening polymer or copolymer [A-2 ], And [A-4] a graft modified product of the above [A-1], [A-2] or [A-3]. 2. The analysis cell according to claim 1, wherein the cyclic olefin resin [A] is an ethylene / cyclic olefin random copolymer [A-1].