JP2001192458A - Method for preserving alicyclic structure-containing polymer resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for exactly selecting a resin required to be heated before molded, which is extremely important in a quality control of the product. SOLUTION: This method for preserving a polymer resin comprises containing the alicyclic structure-containing polymer resin and at least either of an oxygen- detecting agent or a moisture-detecting agent together in a hermetically sealed container. Besides, a method of production comprises judging whether a pretreatment of the preserved resin is needed or not by a variation of color in the oxygen-detecting agent or the moisture-detecting agent, carrying out the pretreatment of the resin when judged to be needed and then molding the polymer resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for preserving an alicyclic structure-containing polymer resin and a method for producing a molded article using the resin. More specifically, the present invention relates to a method for producing a molded article when producing the molded article. The present invention relates to a preservation method capable of judging the necessity of deoxygenation treatment of a product and a production method including the judging step.

[0002]

2. Description of the Related Art Polymer resins having an alicyclic structure such as norbornene resins are widely used as optical materials because of their excellent transparency, low birefringence, and excellent heat resistance. 240517, JP-B-57-8815). Since the norbornene-based resin has a high melting temperature, molding at a high temperature is necessary. Therefore, the molded article may be colored due to the heat history. Such coloring of the molded article during the molding process can be prevented to some extent by performing the molding process in a nitrogen atmosphere (Japanese Patent Publication No. 4-70318).

[0003] The alicyclic structure-containing polymer resin is generally formed into pellets or the like, and is filled with an inert gas in a sealed container such as a bag, a container, a storage can or a tank made of various materials. While stored, the amount of oxygen contained in the pellets (hereinafter, referred to as “dissolved oxygen amount”) may increase during storage, or may be affected by moisture in the storage container, If such pellets are molded as they are, the molded product may be colored or silver streaks or voids may occur. When such a resin having a large amount of dissolved oxygen is used, even if the molding is performed under an inert gas, it is not possible to prevent the occurrence of coloring and silver streaks.

On the other hand, even if such a resin is subjected to a deoxidation treatment or a dehydration treatment such as heat treatment or vacuum drying before molding to remove oxygen and moisture contained in the resin, the molded product is colored. Can be prevented. However, measuring the amount of oxygen and water in the resin requires time and effort, and thus measuring the amount of oxygen and water in the resin before molding complicates the process. Further, it is not necessary to perform a deoxidation treatment or a dehydration treatment on all the resins before molding. Under such circumstances, there has been a demand for a method of presuming whether or not coloring of a molded article occurs before molding and performing quality control of a resin material more easily and accurately.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preserving an alicyclic structure-containing polymer resin material which can more easily and accurately control the quality of the resin material. In addition, by estimating whether or not coloring of the molded article occurs, it is easier and more accurate to determine whether or not to perform a pre-treatment such as deoxygenation treatment or dehydration treatment on the resin material, and to perform coloring of the molded article, etc. It is to provide a method to prevent this.

[0006]

Means for Solving the Problems As a result of repeated studies to solve the above problems, the present inventors have found that the dissolved oxygen and the amount of water in the alicyclic structure-containing polymer resin cause coloring of molded articles. The present invention has been completed by paying attention to the fact that the dissolved oxygen concentration and the water content are proportional to the oxygen concentration and the water concentration in the sealed container for storage.

That is, the present invention relates to a method for coexisting an alicyclic structure-containing polymer resin and an oxygen detecting agent and / or a moisture detecting agent and storing them in a sealed container,
Further, the preserving step (1), a judging step (2) for judging the necessity of deoxidation treatment or dehydration treatment of the polymer resin based on a detection result by the oxygen detector or the moisture detector, If you determine that dehydration is necessary,
The present invention relates to a method for producing an alicyclic structure-containing polymer resin molded article, which comprises a pretreatment step (3) of performing a deoxidation treatment or a dehydration treatment of the polymer resin and a molding step (4) of molding the polymer resin. .

The oxygen detector contains a redox indicator dye and a reducing agent. The reducing agent is preferably either a reducing saccharide or a solid basic substance. It is preferable that the composition contains a cobalt salt. Further, in the above-mentioned storage method, it is preferable to further include a deoxidizing agent and a dehydrating agent. It is preferable that the determination step includes observing a change in the oxygen detecting agent or the moisture detecting agent, and determining the necessity of pretreatment based on the change in the detecting agent. Furthermore, it is preferable that the pretreatment step performed as necessary is one in which heating or vacuum drying is performed.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Alicyclic structure-containing polymer resin The alicyclic structure-containing polymer resin stored in the present invention,
It is usually stored in the form of pellets or the like, and is formed into various molded articles depending on the application.

The preservation method of the present invention is suitable for preserving an alicyclic structure-containing polymer resin having an alicyclic structure in a main chain and / or a side chain. Particularly suitable for the storage of those containing cyclic structures. Specifically, the alicyclic structure referred to herein is a cycloalkane structure, and the number of carbon atoms constituting the alicyclic structure is usually 4 to 30.
In the case where the number of resins, preferably in the range of 5 to 20 resins, is stored, the effect of preventing coloring and the like is enhanced. Such a resin contains a repeating unit having an alicyclic structure in an amount of usually 50% by weight or more, preferably 70% by weight or more from the viewpoint of transparency and heat resistance.

Specific examples of such alicyclic structure-containing polymer resins include, for example, (1) norbornene-based polymers,
(2) a monocyclic cycloolefin polymer, (3) a cyclic conjugated diene polymer, (4) a vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. The preservation method of the present invention is suitable for preservation of norbornene-based polymers, cyclic conjugated diene-based polymers and hydrogenated products thereof among these, and heat-resistant, preservation of norbornene-based polymers excellent in mechanical strength. Especially suitable for

(1) Norbornene-based polymer The norbornene-based polymer is a known polymer disclosed in, for example, JP-A-3-4882 and JP-A-3-122137. Examples thereof include ring-opening polymers of norbornene-based monomers and hydrogenated products thereof, addition polymers of norbornene-based monomers, and addition copolymers of norbornene-based monomers and vinyl compounds.

Specific examples of the norbornene monomer used for the polymerization include bicyclo [2.2.1] -hept-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.
2.1] -Hept-2-ene, 5,5-dimethyl-bicyclo
[2.2.1] -Hept-2-ene, 5-ethyl-bicyclo [2.
2.1] -Hept-2-ene, 5-butyl-bicyclo [2.2.
1] -Hept-2-ene, 5-hexyl-bicyclo [2.2.
1] -Hept-2-ene, 5-octyl-bicyclo [2.2.
1] -Hept-2-ene, 5-octadecyl-bicyclo
[2.2.1] -Hept-2-ene, 5-ethylidene-bicyclo [2.2.1] -hept-2-ene, 5-methylidene-bicyclo [2.2.1] -hept-2-ene, 5-vinyl- Bicyclo [2.2.1] -hept-2-ene, 5-propenyl-bicyclo [2.2.1] -hept-2-ene,

5-methoxy-carbonyl-bicyclo [2.
2.1] -Hept-2-ene, 5-cyano-bicyclo [2.2.
1] -hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-methoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5 -Ethoxycarbonyl-bicyclo [2.2.1] -hept-2-ene, 5-methyl-5-ethoxycarbonyl-
Bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1]
-Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] -hept-5-enyl-2-methyloctanoate,

Bicyclo [2.2.1] -hept-2-ene-5,6
-Dicarboxylic anhydride, 5-hydroxymethyl-bicyclo [2.2.1] -hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2.2.1] -hept-2-ene, 5-hydroxy -I-propyl-bicyclo [2.2.1] -hept-
2-ene, 5,6-dicarboxy-bicyclo [2.2.1] -hept-2-ene, bicyclo [2.2.1] -hept-2-ene-
5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] -hept-2-ene, 5-cyclohexenyl-bicyclo [2.2 .1] -Hept-2-ene, 5
-Phenyl-bicyclo [2.2.1] -hept-2-ene,

Tricyclo [4.3.1^2,5.0^1,6] -Deca-3,7-
Diene (common name dicyclopentadiene), tricyclo
[4.3.1^2,5.0^1,6] -Dec-3-ene, tricyclo [4.4.1
^2,5.0^{1, 6}] -Undeca-3,7-diene or tricyclo
[4.4.1^2,5.0^1,6] -Undeca-3,8-diene, tricyclo
[4.4.1^2,5.0^1,6] -Undec-3-ene, tetracyclo
[7.4.1^10,13.0^1,9.0^2,7] -Trideca-2,4,6-11-tetra
Raen (1,4-methano-1,4,4a, 9a-tetrahydrofluoro
Len)), tetracyclo [8.4.1^11,14.0^1,10.
0 ^3,8] -Tetradeca-3,5,7,12-11-tetraene (1,4-
Methano-1,4,4a, 5,10,10a-hexahydroanthracene
Norbornane having no norbornane ring
Monomer

[0017] tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene (also simply referred to as tetracyclododecene), 8
- methyl - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca -
3-ene, 8-methyl-tetracyclo [4.4.1 ^{2,5.1 7,10} .
0] -Dodeca-3-ene, 8-ethyl-tetracyclo [4.
4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8-methylidene - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8- ethylidene - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0]
-Dodeca-3-ene, 8-vinyl-tetracyclo [4.4.1
^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8-propenyl - tetracyclo [4.4.1 ^{2 5} .1 ^7,10 .0] - dodeca-3-ene,

[0018] 8-methoxycarbonyloxy - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8-methyl-8-methoxycarbonyl - tetracyclo [4.4.1 ^2,5 .1
^7,10.0 ] -Dodeca-3-ene, 8-hydroxymethyl-
Tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene,
8-carboxy - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene,

8-cyclopentyl-tetracyclo [4.4.1
^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8-cyclohexyl - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene, 8-cyclohexenyl - Tetracyclo [4.4.1 ^2,5.1
7,10 .0] - dodeca-3-ene, 8-phenyl - tetracyclo [4.4.1 ^2,5 .1 ^7,10 .0] - dodeca-3-ene, pentacyclo [6.5.1 ^1,8 .1 . ^3,6 .0 ^2,7 0 ^9,13] - pentadeca 3,10
- diene, pentacyclo [7.4.1 ^3,6 .1 ^10,13 .0 ^1,9 .0 ^2,7]
And norbornene-based monomers having a norbornane ring such as -pentadeca-4,11-diene.
The above norbornene monomers can be used alone or in combination of two or more.

In the present invention, in addition to the above norbornene-based monomers, copolymerizable monomers include, for example,
Ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 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-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1
An α-olefin having 2 to 20 carbon atoms, such as eicosene;

Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7- Cycloolefins such as methano-1H-indene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; be able to. These copolymerizable monomers can be used alone or in combination of two or more.

The ring-opening polymer of the above-mentioned monomer is used as a ring-opening polymerization catalyst as a catalyst system comprising a halide, nitrate or acetylacetone compound of a metal such as ruthenium, rhodium, palladium, osmium, iridium or platinum, and a reducing agent; Alternatively, titanium, vanadium, zirconium, tungsten, a metal halide such as molybdenum or an acetylacetone compound, using a catalyst system consisting of an organoaluminum compound, in a solvent or without a solvent, usually at -50 ℃ ~ 100 ℃ It can be obtained by ring-opening polymerization at a polymerization temperature and a polymerization pressure of 0 to 50 kg / cm ² . Hydrogenated norbornene-based polymer, according to a conventional method,
It can be obtained by a method of hydrogenating a ring-opened (co) polymer with hydrogen in the presence of a hydrogenation catalyst.

An addition copolymer of a norbornene-based monomer and the above-mentioned copolymerizable monomer is, for example, a catalyst system comprising a monomer component in a solvent or without a solvent comprising a titanium, zirconium or vanadium compound and an organoaluminum compound. In the presence of the compound (A), the copolymerization can be usually carried out at a polymerization temperature of -50 ° C to 100 ° C and a polymerization pressure of 0 to 50 kg / cm ² .

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cyclic olefin polymer include monocyclic cycloolefin polymers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. Can be used. (3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, JP-A-6-13
Cyclopentadiene disclosed in 6057 and JP-A-7-258318, a polymer obtained by 1,2- or 1,4-addition polymerization of a cyclic conjugated diene-based monomer such as cyclohexadiene, and a hydrogenated product thereof Etc. can be used.

(4) Vinyl alicyclic hydrocarbon-based polymer Examples of the vinyl alicyclic hydrocarbon-based polymer include vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. Polymer of alicyclic hydrocarbon monomer and hydrogenated product thereof, JP-A-63-43910
And hydrogenated products of the aromatic ring portion of a polymer of a vinyl aromatic monomer such as styrene and α-methylstyrene disclosed in JP-A-64-1706 and the like. The configuration of these vinyl alicyclic hydrocarbon polymers may be any of atactic, isotactic, and syndiotactic. For example, any of 0 to 100% in syndiotacticity by dyad display. Can also be used.

The molecular weight of the alicyclic structure-containing polymer resin to be preserved by the method of the present invention is appropriately selected according to the purpose of use. In weight average molecular weight in terms of polyisoprene measured by permeation chromatography, 5,000 to 500,000, preferably 8,000 to 200,000,
More preferably, it is in the range of 10,000 to 100,000. Because mechanical strength and formability are highly balanced,
Those in the range of 100 to 100,000 are often used. The glass transition temperature (T
g) may be appropriately selected depending on the purpose of use, but is usually 50 to 300 ° C, preferably 60 to 200 ° C, more preferably 70 to 300 ° C.
~ 180 ° C.

Oxygen Detecting Agent The oxygen detecting agent used in the present invention has a property of indicating whether or not it has come into contact with a certain amount or more of oxygen, and usually contains a composition containing a redox indicator dye and a reducing agent. Made of things. An oxidation-reduction indicator dye is a compound in which the color tone of an oxidation type and that of a reduction type are remarkably different, and are rapidly oxidized or reduced at a certain oxidation-reduction potential to change color. Specifically, methylene blue and its complex salts, thiazine dyes such as new methylene blue, indigo dyes such as potassium indigosulfonate, thioindigo dyes such as thioindico and its chloro derivative, and indica such as 2,6-dichloroindophenol Examples include phenolic dyes, and salts thereof, rous violet, methylene green, and the like.

The reducing agent used in the oxygen detecting agent refers to a reducing agent which gives electrons to another substance and oxidizes itself, and which has an oxidation-reduction potential difference enough to cause the indicator to change its color. . Specific examples include reducing saccharides and solid basic substances. Reducing sugars (reducing sugars)
Are monosaccharides and oligosaccharides in which the carbon atom at the 1-position of aldose or the 2-position of ketose, that is, the anomeric carbon atom has not been substituted. Means something. Specific examples include D-glucose, D-xylose, D-fructose, D-lactose, D-galactose, and the like.

The solid basic substance is a compound which reacts with oxygen in the air in a solid state, for example, phosphoric acid, phosphorous acid,
Examples thereof include alkali metal salts of weak acids such as hypophosphorous acid, carbonic acid, silicic acid, boric acid and organic acids, or alkaline earth metal salts thereof. Specifically, ascorbic acid or a salt thereof, isoascorbic acid or a salt thereof, butylhydroxyanisole, pyruvic acid or a salt thereof, phosphite, hypophosphite, sulfite, thiourea dioxide,
Rongalits (sodium hydroxymethanesulfinate), nitrite, borohydride, thioglycolate, bicarbonate and the like. Among the above reducing agents, it is preferable to use reducing saccharides from the viewpoints of decoloring speed, stability, and harmlessness to the human body, and specifically, D-glucose, D-fructose, D-fructose, and the like. -Maltose and the like.

Commercially available products such as Ageless Eye (manufactured by Mitsubishi Gas Chemical Co., Ltd.) and Secur K (manufactured by Nippon Soda Co., Ltd.) may be used as such an oxygen detecting agent, or may be synthesized as follows. Is also good. For example, a predetermined amount of 2,6-
Dichloro-3′-methylindophenol sodium salt is dissolved in warm water to obtain a solution (1), and a predetermined amount of red
No. 2 is dissolved in warm water to obtain a solution (2). A predetermined amount of sodium bicarbonate, fructose and polyethylene glycol are dissolved in warm water to obtain a solution (3). Dissolution (1)-
(3) is mixed, and an appropriate cloth is immersed in the mixed liquid and dried to prepare an oxygen detector sheet. This sheet can be processed into a disk, square or other shape of a predetermined size, and wrapped with, for example, a film of polyethylene or the like to provide an oxygen detecting agent.

A suitable amount of a liquid oxygen detector may be applied to the inside of a resin storage bag. In such a case,
In order to maintain the adhesiveness of the main agent of the oxygen detector and the dye on the inner surface of the storage bag, the above-mentioned mixed solution includes, for example, ethyl cellulose, polyvinyl alcohol, a binder such as starch, calcium carbonate, titanium oxide, and barium sulfate. It is preferable to add a pigment such as If necessary, a polyhydric alcohol such as glycerin or polyethylene glycol may be added.

The oxygen detector used in the present invention is not limited to a liquid, and may be made into a tablet by adding an appropriate filler or other components. Fillers added to maintain tablet strength include inorganic fillers such as silicates and organic fillers such as various polymers, and any of them may be used. When a tablet is used as the oxygen detector, a lubricant such as a stearate may be further added.

Moisture Detector The moisture detector used in the present invention is a substance having a property of changing its color when it comes into contact with a certain amount or more of water. For example, it is composed of a composition containing (1) a metal salt, (2) a redox indicator dye, and (3) a moisture absorbent. As metal salts, cobalt chloride, cobalt bromide, cobalt sulfate,
Cobalt salts such as cobalt carbonate; halides such as iron chloride, copper chloride, nickel chloride, iron bromide, and manganese bromide; magnesium chloride, strontium chloride, calcium chloride, barium chloride, magnesium nitrate, calcium nitrate, barium nitrate Alkaline earth metal salts; manganese iodide, nickel sulfide, manganese sulfate and the like.

Among the above-mentioned cobalt salts, a water-soluble cobalt salt is particularly used, and a cobalt halide such as cobalt chloride or cobalt bromide is preferably used in view of discoloration property and discoloration speed. Further, among the alkaline earth metals, a water-soluble salt (particularly calcium chloride) is preferable.
Examples of the redox indicator include basic dyes such as brilliant green and crystal violet.

Such a moisture detecting agent is available from HUMITECTOR INNDI
A commercially available product such as CATOR CARD (manufactured by HUMIDIAL) may be used, or may be synthesized as follows. For example, an aqueous solution of cobalt chloride may be prepared, the solution may be impregnated into filter paper, and then dried to purify the cobalt salts, and a redox indicator dye and a moisture absorbent may be added thereto. In addition, an alkaline earth metal surfactant, a pigment, and the like may be added in order to control color development, color shade, and the like.

Further, in the present invention, an atmosphere detector may be used in addition to the oxygen detector and the moisture detector. The atmosphere detector may be any agent that detects the atmosphere state by a detachable color, discoloration, etc., and in addition to the moisture detector, the oxygen detector, a carbon dioxide detector, an alcohol detector, and the like.
Any substance that can detect a substance that has an adverse effect on molding processing may be appropriately selected and used. The shape of the atmosphere detecting agent may be appropriately selected depending on the method of storing the resin, and a shape such as a powder, a tablet, and a sheet is usually used.

Sealed Container The sealed container used in the present invention is not particularly limited depending on the material or the shape. The polymer resin is filled in a sealed container,
After the air in the container is replaced with an inert gas such as nitrogen gas, the air in the container may be shielded from the outside air by a heat seal, various tapes, clips, a sealing material such as a string, a lid, or the like. preferable. When the container is formed in a bag shape, an inner bag of a paper bag may be used as a sealed container.

As the material of the container, for example, a material having a high oxygen barrier property such as a polyethylene film coated with vinylidene chloride or a polyethylene film deposited with silicon oxide, polyethylene, polypropylene, silicone resin, vinyl acetate and polyethylene Any of oxygen-permeable materials such as the above can be used. here,
Materials with high oxygen barrier properties have an oxygen permeability of 200 mL / m ²
The material having an oxygen permeability of 200 d / m ² · day · atm means a material having an oxygen permeability of not more than day · atm.

The above various materials can be used alone, two or more materials can be used as a composition, or they can be used by laminating. For example, when a paper bag is used as an outer layer and a bag made of the above material is used as an inner layer, the light-shielding property is improved, so that light deterioration of the alicyclic structure-containing polymer resin can be reduced. Further, a container made of a laminated body of resins having improved light-shielding properties by adding a pigment can be suitably used for the same reason.

When using containers made of wood, ceramics, metal or the like, these containers may be used as they are, but the inner surface of the container is made of the above-mentioned oxygen barrier or oxygen permeable material. The laminated sheets may be used with an adhesive or the like. Also, these sheets are made into bags,
It can also be used as an inner bag, and the above material can be dissolved in a solvent or the like to form a coating material, which can be used by coating the inner surface of the container. The shape of the container may be appropriately selected in consideration of various factors such as space, bulkiness, and ease of transportation during storage.

In the storage method of the present invention, the above-mentioned various materials are formed into a sheet shape and processed into a bag shape, or a tray-type or container-type container with a lid or the like can be suitably used. In the sealed container as described above, without opening the container, for example, to observe the atmosphere detecting agent coexisting with the resin, the entire container is transparent, or at least a part of the container is provided with a transparent portion Preferably. Further, it is preferable to arrange the atmosphere detecting agent in the container so that the agent can be observed from the transparent portion.

For example, a pocket is provided in this transparent part,
A tablet-type atmosphere detecting agent may be added, a liquid-state atmosphere detecting agent may be applied in advance to the inside of the transparent portion, or a sheet-like atmosphere detecting agent may be adhered to observe the change. In such an observable mode, when a change in the atmosphere detecting agent is observed during storage, the container is opened once, and if necessary, a deoxidizing agent or a dehydrating agent is added, or A pretreatment such as a deoxygenation treatment or a dehydration treatment is performed, and after the air in the container is replaced with an inert gas, the container can be sealed again.

[0043] The oxygen scavenger deoxidizer, refers to one that absorbs oxygen in the air by oxidation of compounds contained therein, depending on the kind of the compound that absorbs oxygen, inorganic oxygen scavenger and organic And oxygen scavengers are known. As the oxygen scavenger, the above-described reducing agent used in the oxygen detector may be used. Inorganic oxygen absorber containing iron powder, sulfite, etc., ascorbic acid, sugar,
Examples include those containing an organic reducing agent such as phenols. These oxygen scavengers are widely available and can be easily obtained.

The oxygen scavenger is usually used in the form of a sphere, a crush, a granule, or the like, or a compression-molded form thereof, and is packaged with a sheet of a thermoplastic resin such as ethylene or polypropylene, synthetic paper, or other paper. . When the oxygen absorber is compression molded into granules, the oxygen absorber, which is a raw material powder,
After adding fillers, binders, etc. and kneading them into a soft lump,
The granules can be formed into granules by a wet granulation method in which granules are passed through a granulator or a sieve, or a granule method in which water-free slug tablets are prepared, crushed, sieved and granulated. When the oxygen absorber is granulated, a filler can be added.Specifically, in order to impart hardness,
It is preferable to add an inorganic filler such as a silicate. Also,
In addition to a binder such as gum arabic and the like, stearates such as a lubricant are appropriately selected and blended, and tableting is performed according to a conventional method.

The shape of the oxygen scavenger is not particularly limited.
The packaging material of the oxygen scavenger is not particularly limited as long as it does not prevent oxygen absorption. In the present invention, the oxygen scavenger and the thermoplastic resin such as polyethylene or polypropylene are mixed at an appropriate ratio according to a conventional method using a twin-screw kneader or a kneader, and are sheet-like or extruded. It may be formed into a film. In the case of a sheet shape or a film shape, it can be formed into a laminate with the above-described sheet material or attached to a portion where oxygen is easily permeable, and can be used in various modes. Examples of such oxygen absorbers include Ageless (produced by Mitsubishi Gas Chemical Co., Ltd.) and Vitalon (produced by Toagosei Co., Ltd.).

Dehydrating agent The dehydrating agent used in the method of the present invention can prevent the adsorption of the water to the resin material (pellet) by adsorbing the water present in the sealed container by vaporization or the like. What is necessary is just to be used, and what is generally used as a desiccant can be used. Specifically, a tablet formed from a hygroscopic solid such as calcium chloride or diphosphorus pentoxide, or a porous substance such as silica gel can be used and can be obtained as a commercial product.

[0047] In storing step present invention, in the sealed container, and alicyclic structure-containing polymer, by the coexistence of the oxygen detecting agent and the moisture detection agent save, the molded article using the resin It is characterized in that the necessity of a pretreatment such as a deoxidation treatment or a dehydration treatment for a resin material can be easily determined at the time of molding. The storage temperature is preferably low, so that oxidation of the resin is not promoted, usually -40 to 50
° C, preferably -20 to 40 ° C, more preferably -10 to 30 ° C
It is.

The atmosphere in the sealed container is preferably an atmosphere having a low oxygen concentration so as not to increase the oxygen concentration in the resin material (pellet), and is preferably replaced with an inert gas such as nitrogen gas. More preferred. In addition, in order to prevent moisture from adsorbing to the pellets, it is preferable that the humidity during storage be low. Further, in order to prevent light-resistant deterioration of the resin material, the sealed container is preferably shielded from light. As described above, the container is provided with a transparent portion (window) for confirming discoloration of the oxygen detector and the like. Even if the window is provided, it is preferable that the window can shield light during storage of the resin.

When the above-mentioned oxygen detecting agent, moisture detecting agent, deoxidizing agent and dehydrating agent coexist in a resin material (pellet) in a sealed container, the detecting agent is buried in the pellet,
It is preferable that the detection agent is placed in a transparent bag or the like so that it is attached to the inside of the container or provided with a pocket so that it is not difficult to confirm or remove the discoloration. However, in order to prevent a difference in oxygen concentration or the like from occurring between the atmosphere in the container and the atmosphere on the surface of the detection agent, it is preferable that the bag or the like containing the detection agent is made of a material having a somewhat high oxygen permeability. Further, if powder or the like is scraped off from the detecting agent, the bag, or the like, the pellet is contaminated.

Judgment Step The judgment step of the present invention is based on the change in color of the above-mentioned detection agent stored in a sealed container together with the alicyclic structure-containing polymer resin.
It is characterized in that it is determined whether or not the resin material is subjected to a deoxidation treatment or a dehydration treatment. More specifically, for example, in the case of an oxygen detector, (1) when the oxygen detector is pink and indicates that the oxygen concentration is low, it is determined that deoxygenation treatment is not necessary. And mold as it is,
(2) When the oxygen detector is purple and indicates that the oxygen concentration is high, the oxygen detection agent is subjected to a heat treatment or a reduced pressure treatment as a deoxygenation treatment and then molded. In the case of a moisture detector, for example, silica gel or the like is used as a detector,
When the blue silica gel changes to pink, dehydration treatment such as heat treatment is performed before molding.

[0051] In the deoxidizing treatment or dehydration treatment the invention, for example, a norbornene resin, an oxygen detecting agent to coexist in the bag, when the color of the oxygen detecting agent is changed, before the molding of the resin Deoxygenation treatment such as heat treatment or reduced pressure treatment is performed. When coexisting with a moisture detecting agent instead of an oxygen detecting agent, a dehydration process is performed, but a heating process or a depressurizing process is actually performed similarly to the deoxidizing process. Hereinafter, the deoxidation treatment, the dehydration treatment, or a combination thereof is referred to as “pretreatment”. When the oxygen detecting agent and the moisture detecting agent are made to coexist with the resin, the pretreatment is performed when at least one of them exhibits the above-mentioned color change.

This pretreatment may be either heat treatment or reduced pressure treatment. Heat treatment and reduced pressure treatment may be performed simultaneously, or both treatments may be performed before or after. In performing the decompression treatment, the oxygen partial pressure is preferably 20 mmHg or less from the viewpoint of preventing coloring of the molded article, and more preferably the vacuum treatment is performed. The temperature in the case of the heat treatment is (Tg-60) to (Tg-5) ° C., preferably (Tg-50) to (Tg-60), where the glass transition temperature of the alicyclic structure-containing polymer resin is (Tg). (Tg-10) ° C, more preferably (Tg-10)
-40) to (Tg-15) ° C. The processing time is 2
~ 48 hours, preferably 4 ~ 24 hours, more preferably 6 ~
12 hours.

In the case of a vacuum treatment, the pressure may be maintained at 1 atm or less for 2 hours or more in an inert gas atmosphere, but when the atmosphere is not an inert gas atmosphere, the oxygen partial pressure is reduced to 20 mmHg or less by reducing the pressure. And hold for at least 2 hours. The above heat treatment, reduced pressure treatment, or vacuum treatment is preferably performed in an atmosphere of an inert gas such as nitrogen. As another method, a deoxidizing agent or a dehydrating agent,
It may be newly placed in the container, or may be additionally added.

In the present invention, as described above, the above-mentioned heat treatment and reduced pressure treatment may be performed simultaneously or in combination, and furthermore, the heat treatment and the pressure reduction treatment may be performed in the presence of an atmosphere adjuster or the like. By performing this pretreatment, it is possible to prevent coloring of the molded article when the oxygen detecting agent is discolored, and to prevent silver streaks and voids when the moisture detecting agent is discolored. Can be.

Forming Step In the forming step of the present invention, the necessity of the pretreatment is judged in the above judgment step, and if it is judged that the pretreatment is necessary, the pretreatment is performed, and then the stored alicyclic structure is stored. Containing polymer resin,
It is characterized by being formed into a molded body. As a molding method, a heat-melt molding method is usually used, and specifically, a molding method such as injection molding, extrusion molding, blow molding, or the like can be used.

[0056]

EXAMPLES The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.

(Example 1) Known metathesis ring-opening polymerization,
And 100 parts of hydrogenated dicyclopentadiene / dimethanooctahydronaphthalene / tetracyclododecene ring-opening copolymer obtained by the hydrogenation reaction, and Irganox 1010 (manufactured by Ciba Geigy) as an antioxidant. 20 kg of the resin pellets obtained by blending 0.2 part was placed in an oven, dried by heating at 110 ° C. for 12 hours, and then cooled. Ageless Eye (Mitsubishi Gas Chemical Co., Ltd.) as oxygen detector
1 bag, 4 bags of ageless as oxygen scavenger, thickness 10
It was placed in a 0 μm polyethylene bag, sealed by heat sealing, and stored at about 25 ° C. for 30 days.

When the bag was opened, the color of the ageless eye, which was an oxygen detecting agent, was pink, indicating that the oxygen concentration was 0.1% or less. Therefore, it was judged that pretreatment of the pellets before molding was unnecessary, and the pellets were directly injection molded at 280 ° C. by an injection molding machine. Table 1 shows the results. From the results in Table 1, it was confirmed that there was no coloring of the molded body, and that the determination as to whether or not to perform the pretreatment based on the change in the color of the oxygen detector was appropriate.

Comparative Example 1 Pellets were stored in the same manner as in Example 1 except that the oxygen detector and the oxygen detector were not added. When the bag was opened, the appearance of the pellets was exactly the same as that stored by the method of Example 1, and it was not possible to determine whether or not pretreatment was necessary. The pellets were injection molded at 280 ° C. using an injection molding machine without performing pretreatment. Table 1 shows the results. As shown in Table 1, the molded article was colored.

Example 2 Pellets were stored in the same manner as in Example 1 except that no oxygen scavenger was added. When the bag was opened, the color of the ageless eye, which was an oxygen detector, was purple, indicating that the oxygen concentration was 0.1% or more. For this reason, it was determined that deoxygenation treatment or dehydration treatment was necessary before molding.

Before molding, heat treatment of the pellets (110 ° C., 4
(Time heating) and those not subjected to the same treatment before molding were injection-molded at 280 ° C. using an injection molding machine. Table 1 shows the results. From the results in Table 1, it was found that neither the coloring of the molded article nor the silver streak was observed in the case where the heat treatment was performed before molding, whereas the coloring of the molded article was observed in the case where the pretreatment was not performed. From the above, it was confirmed that the judgment based on the change in the color of the oxygen detector was appropriate.

(Example 3) A bag for storage was changed to a bag made of ethylene vinyl alcohol copolymer (hereinafter abbreviated as "EVOH") having a thickness of 40 µm, and no oxygen scavenger was added. The pellet was stored in the same manner as in 1. When the bag was opened, the color of the ageless eye, which was an oxygen detector, was pink, indicating that the oxygen concentration was 0.1% or less. Therefore, it was determined that pretreatment of the pellet before molding was unnecessary, and the pellet was injection molded at 280 ° C. by an injection molding machine without performing the pretreatment. Table 1 shows the results.
As shown in Table 1, neither coloring nor silver streak was observed in the molded article.

Example 4 The same procedure as in Example 1 was carried out except that silica gel (blue) was used as a moisture detector instead of the oxygen detector. When I opened the bag,
The color of the silica gel was pink, and it was confirmed that the silica gel adsorbed moisture. Therefore, the pellets that had been subjected to heat treatment (heating at 110 ° C. for 4 hours) before molding and those that had not been subjected to the same heat treatment before molding were each subjected to 28 injection molding machines.
Injection molding was performed at 0 ° C. Table 1 shows the results.

From the results shown in Table 1, it was confirmed that in the case where the heat treatment was performed before molding, the molded article was neither colored nor silver streaked, and the judgment based on the change in the color of the moisture detecting agent was appropriate. Was. On the other hand, silver streaks were observed in the case where the pretreatment was not performed.

[0065]

[Table 1]

[0066]

According to the method of the present invention, when the alicyclic structure-containing polymer resin is stored, it is possible to easily and accurately judge whether pretreatment is necessary or not.
In this way, the resin that needs pretreatment is sorted and processed,
Coloring and silver streaks of the molded product can be efficiently prevented.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23:18 C08L 23:18 45:00 45:00 65:00 65:00 F term (reference) 4F070 AA12 AA68 AC20 AC22 AC40 AC42 AC49 AC50 AC59 AE03 BB03 BB08 4F071 AA21 AB08A AB24A AC09A AC11A AC20A AG20 AG31 BA01 BB05 BB06 4F201 AA03 AB01 AC01 BA04 BC01 BC12 BC19 BC37 BN22 BN44 BN50 BQ01

Claims (6)

[Claims] 1. A method for preserving an alicyclic structure-containing polymer resin, comprising coexisting an alicyclic structure-containing polymer resin and an oxygen detector and / or a moisture detector in a sealed container. 2. A preservation step (1) in which an alicyclic structure-containing polymer resin and an oxygen detecting agent and / or a moisture detecting agent coexist and are stored in a sealed container, and a detection result by the oxygen detecting agent or the moisture detecting agent. (2) determining the necessity of deoxidation or dehydration treatment of the polymer resin on the basis of the above. If it is determined that deoxygenation treatment or dehydration treatment is necessary, the deoxygenation treatment of the polymer resin is determined. Alternatively, a method for producing an alicyclic structure-containing polymer resin molded article, comprising a pretreatment step (3) of performing a dehydration treatment and a molding step (4) of molding the polymer resin. 3. The method for preserving an alicyclic structure-containing polymer resin according to claim 1, wherein the oxygen detector is a composition containing a redox indicator dye and a reducing agent. 4. The method for preserving an alicyclic structure-containing polymer resin according to claim 1, wherein the moisture detector is a composition containing a cobalt salt. 5. The method for preserving an alicyclic structure-containing polymer resin according to claim 1, further comprising a deoxidizer. 6. The determination step (2) is to observe the color of the oxygen detector and / or the moisture detector and determine the necessity of deoxygenation or dehydration based on the color. Item 3. The production method according to Item 2.