JP2001277430A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate capable of further enhancing the strength, gas permeability or the like of a norbornene type polymer by performing the co-extrusion processing of the norbornene type polymer excellent in heat resistance, waterproofness, strength or the like and other resin. SOLUTION: The laminate consists of (A) the thermoplastic norbornene type polymer and (B) at least one resin selected from among the group consisting of other olefinic resin, a polyester resin and a halogenated hydrocarbon resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a laminate obtained by subjecting a thermoplastic norbornene-based polymer to other olefin-based resin, polyester resin, halogenated hydrocarbon-based resin, etc., by co-extrusion or lamination. About. The laminate of the present invention is one in which the strength, gas permeability, and the like of the norbornene-based polymer are supplemented by coextrusion processing or lamination processing with another resin.

[0002]

2. Description of the Related Art Generally, polyolefin-based polymers are
Because it has a structure consisting of only carbon and hydrogen and no unsaturated bond, it has low affinity for water, does not absorb or transmit moisture,
Further, it has a feature of high resistance to acids, alkalis, other chemicals and various solvents. Typical examples are polyethylene and polypropylene, which are formed into sheets, films, cylinders or rods by melt extrusion and used for a wide range of applications. However, these conventional materials have insufficient heat resistance, and have a drawback that they are deformed by heating at a relatively low temperature of 70 to 80 ° C. or lower, and cannot be used at higher temperatures. In addition, these materials had poor transparency and could not be used for optical applications.

On the other hand, for example, polycarbonate (PC) and polymethyl methacrylate (PMMA) have been mainly used as transparent plastic molding materials for optics such as optical disk substrates and plastic lenses. However, PC has a large birefringence, and PMMA has a large water absorption and an insufficient heat resistance, which makes it difficult to meet increasingly sophisticated requirements.

Recently, thermoplastic saturated norbornene-based polymers, such as hydrogenated ring-opening polymers of norbornene-based monomers and addition polymers of norbornene-based monomers and ethylene, have attracted attention as optical plastic molding materials for optical disk substrates and the like. (Japanese Patent Laid-Open No. 60-2)
No. 6024, JP-A-64-24826, JP-A-60-
168708, JP-A-61-115912, JP-A-61-120816, etc.).

These thermoplastic saturated norbornene-based polymers are a kind of polyolefin-based polymer, exhibit excellent water resistance, chemical resistance, and solvent resistance like other polyolefins, and have a high glass transition temperature of 100 ° C. or higher. It is a highly transparent material that can synthesize a heat-resistant polymer and has a total light transmittance of 90% or more.

[0006] From the above, the thermoplastic saturated norbornene-based polymer can be used not only as a heat-resistant polyolefin material for various uses, but also with small birefringence and excellent transparency, water resistance and heat resistance. As a transparent material that also has, it can be developed for optical applications and the like.

However, these thermoplastic saturated norbornene-based polymers are brittle as compared with polyethylene, polypropylene, and PMMA, and when extruded into sheets, films, or rods, they are easily broken or broken, and a sufficient strength is not obtained. In addition, there are also problems that foam-like defects often occur in the extruded product, appear as visually streaks on the surface, and further reduce the strength. In addition, even if there is no visible large streak, when observing in detail using an optical microscope etc.,
Fine voids and crack-like defects (hereinafter, referred to as “microvoids”) that are invisible to the naked eye often occur in the interior. Until now, in the extrusion molding of thermoplastic saturated norbornene-based polymers, a molded product without any microvoids has been used. Had not been obtained.

As another method for obtaining a sheet-like or film-like molded article, there is a casting method in which a polymer is cast as a solution of an appropriate solvent and the solvent is evaporated. According to this method, a molded article having almost no microvoids is obtained. can get. However, even in the case of a molded product having a thickness of about several μm, the solvent does not completely evaporate and remains for about several percent, so that sufficient strength cannot be obtained, or the Each time the residual solvent evaporates, the characteristics of the molded article change, or the evaporated solvent adversely affects other components incorporated around the molded article. A film or sheet-like molded product requires a tensile strength of 800 kg / cm ² or more, preferably 900 kg / cm ² or more from the viewpoint of durability, but a cast material having such a sufficient strength is required. Not obtained.

Therefore, conventionally, a sheet-like or film-like molded article made of a thermoplastic saturated norbornene-based polymer has no fine voids or crack-like defects, and has a tensile strength of 800 kg / cm ² or more. It is not provided with strong strength.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to co-extrude a norbornene-based polymer having excellent heat resistance, water resistance, strength and the like with another resin to obtain the strength of the norbornene-based polymer. It is an object of the present invention to provide a laminate that can further supplement gas permeability and the like.

Another object of the present invention is to provide a thermoplastic norbornene-based polymer and other resins which are excellent in heat resistance, water resistance, strength and the like and can provide a molded article free from defects such as microvoids, foams, and streaks. And to provide a laminate comprising:

The present inventors have conducted intensive studies to solve the above problems, and as a result, are selected from the group consisting of thermoplastic norbornene-based polymers and other olefin-based resins, polyester resins, and halogenated hydrocarbon-based resins. The inventors conceived of a laminate comprising at least one kind of resin. Such a laminate can be obtained by coextrusion processing, lamination processing, or the like. The present invention has been completed based on these findings.

[0013]

According to the present invention, (A) a thermoplastic norbornene-based polymer and (B)
A laminate comprising at least one resin selected from the group consisting of other olefin-based resins, polyester resins, and halogenated hydrocarbon-based resins is provided. According to the present invention, the following aspects are provided.

1. The above laminate obtained by coextrusion or lamination. 2. The laminate described above, which is obtained by co-extrusion when extruding a norbornene-based polymer into a sheet or film. 3. The above laminate obtained by extruding a norbornene-based polymer into a sheet-like molded product and further performing co-extrusion during the extrusion in the case of stretching in a uniaxial or biaxial direction. 4. The above laminate, which is a packaging film or a container. 5. The above laminate, wherein the thermoplastic norbornene-based polymer is a thermoplastic saturated norbornene-based polymer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (1) Thermoplastic norbornene-based polymer The molding material targeted by the present invention is a thermoplastic norbornene-based polymer, typically a thermoplastic saturated norbornene-based polymer, and specific examples thereof include the following general formula [I] And / or a polymer having a structural unit represented by [II]. General formula [I]

[0016]

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Wherein R ₁ and R ₂ are hydrogen,
The hydrocarbon residue or a polar group such as halogen, ester, nitrile and pyridyl may be the same or different, and R ₁ and R ₂ may form a ring with each other. n is a positive integer. q is 0 or a positive integer. General formula [II]

[0018]

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Wherein R ₃ and R ₄ are hydrogen,
The hydrocarbon residue or a polar group such as halogen, ester, nitrile, pyridyl and the like may be the same or different, and R ₃ and R ₄ may form a ring with each other. l and m are positive integers. p is 0 or a positive integer. ]

The polymer having the structural unit represented by the general formula [I] includes, as monomers, for example, norbornene, and its alkyl and / or alkylidene-substituted product;
For example, 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-
2-norbornene and the like; dicyclopentadiene, 2,3-
Dihydrodicyclopentadiene, an alkyl-substituted product thereof such as methyl, ethyl, propyl, and butyl, and a polar-substituted product such as halogen; dimethanooctahydronaphthalene, its alkyl and / or alkylidene-substituted product;
And polar group substituents such as halogen, for example, 6-methyl-1,4: 5,8-dimetano-1,4,4a, 5,6.
7,8,8a-octahydronaphthalene, 6-ethyl-
1,4: 5,8-dimethano-1,4,4a, 5,6
7,8,8a-octahydronaphthalene, 6-ethylidene-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimetano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5
6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5,8-dimethano-1,4,
4a, 5,6,7,8,8a-octahydronaphthalene and the like; cyclopentadiene trimer to tetramer, for example, 4,
9: 5,8-Dimethano-3a, 4,4a, 5,8,8
a, 9,9a-octahydro-1H-benzondene,
4,11: 5,10: 6,9-trimethano-3a, 4,4
4a, 5, 5a, 6, 9, 9a, 10, 10a, 11,
11a-dodecahydro-1H-cyclopentaanthracene or the like is used, and the ring-opened polymer obtained by polymerization by one or more known ring-opening polymerization methods is hydrogenated by an ordinary hydrogenation method. Is a saturated polymer. Hydrogenated ring-opening polymer (saturated polymer)
To make the glass transition temperature (Tg) of 100 ° C. or higher,
Among these norbornene-based monomers, tetracyclic or 5
It is preferable to use a cyclic compound, or to use these as a main component and to use them together with a bicyclic or tricyclic monomer. In particular,
From the viewpoint of birefringence, it is preferable to use a tetracyclic lower alkyl-substituted or alkenyl-substituted compound as a main component.

The polymer having the structural unit represented by the general formula [II] is a polymer obtained by addition-copolymerizing, as a monomer, one or more of the above-mentioned norbornene monomers and ethylene by a known method. And / or hydrogenated products thereof, all of which are saturated polymers.

The thermoplastic norbornene-based monomer is prepared by allowing an α-olefin such as 1-butene, 1-pentene, 1-hexene or the like to be present as a molecular weight regulator in the production process of the polymers [I] and [II]. Alternatively, a polymer copolymerized by adding a small amount of other monomer components such as cyclopropene, cyclobutene, cyclopentene, cycloheptene, cyclooctene, and cycloolefin such as 5,6-dihydrocyclopentadiene may be used. Absent.

The thermoplastic norbornene-based polymer in the present invention has a number average molecular weight (M) measured by high performance liquid chromatography (HLC) analysis using toluene as a solvent.
n) is from 50,000 to 500,000, preferably 6
000-200,000, weight average molecular weight (Mw)
Is 100,000 to 2,000,000, preferably 1
Preferably, the molecular weight distribution (Mw / Mn) is at least 2.2.

When Mn and Mw are smaller than the above ranges,
When a film, sheet, rod, or the like is formed by extrusion, a molded product having sufficient strength cannot be obtained. Conversely, if it is larger than this range, the moldability will be poor, and molding will be difficult even when used for extrusion because of too high viscosity. Further, even if the solution is dissolved in an appropriate solvent and cast or spun, the solubility in the solvent is insufficient. In addition, it is difficult to control the synthesis reaction of such a high molecular weight polymer, and there is a disadvantage that a material having stable quality cannot be obtained.
Further, the molecular weight distribution (Mw / Mn) is preferably 2.2 or more, more preferably 2.4 or more, and particularly preferably 2.8 or more.

In general, it is considered that a thermoplastic polymer having a smaller molecular weight distribution and being closer to monodisperse has a better balance between strength and moldability and has better performance. However, when a polymer having a relatively large molecular weight is extruded as in the present invention, for example, into a sheet or film,
In the process of cooling and solidifying from the molten state, monodisperse molecules harden instantaneously at a certain temperature instantaneously, rather than the case where molecules of various molecular weights gradually solidify in order from the larger molecular weight, No residual stress,
A flat and clean molded product can be obtained as a whole. This tendency is particularly remarkable in the thermoplastic norbornene-based polymer because the polymer is rigid, has high heat resistance, and has a considerably high molding temperature of around 300 ° C. Therefore, for the purpose of the present invention, the molecular weight distribution is preferably 2.2 or more, more preferably 2.4 or more, and particularly preferably 2.8 or more. If the molecular weight distribution is smaller than this range, extrusion molding is difficult, and it is difficult to obtain a molded article having good smoothness and optical characteristics.

As the molecular weight distribution (Mw / Mn) increases, the moldability improves. In general, when a polymer having high heat resistance and high rigidity such as polycarbonate is rapidly cooled from a molten state, internal deformation occurs and a phenomenon that a flat molded product cannot be obtained easily occurs. The same applies to thermoplastic norbornene-based polymers. For example, when extruding from a T-die with an extruder and pulling the sheet, a phenomenon occurs in which a flat sheet cannot be pulled unless the temperature of the roll is increased. Tg is 14
In the case of a polymer of about 0 ° C., the roll temperature is set
By raising the temperature to 0 ° C., the sheet can be pulled flat. However, usually, the heating of the roll is often by water,
In many cases, the temperature of the roll can be raised only up to about 90 ° C.

When the molecular weight distribution is less than 2.2, the roll cannot be formed well even if the temperature of the roll is raised to about 140 ° C., which is close to the glass transition temperature of the polymer. By raising the temperature, a flat molded product can be formed. Further, when the molecular weight distribution spreads to 2.8 or more, the moldability is further improved, and a molded product which is flat and has no internal distortion even at a roll temperature of about 90 to 100 ° C. can be obtained. The upper limit of the molecular weight distribution is not particularly limited, but if it is too large, Mn is large, and sufficient strength cannot be obtained for a high melt viscosity, and the synthesis of such a polymer itself becomes difficult. , Approximately 6.0 or less is preferable.

A thermoplastic norbornene-based polymer having such a molecular weight (Mn, Mw) and molecular weight distribution (Mw / Mn) can be used in a synthesis reaction, for example, by adjusting the amount of a catalyst used or changing the polymerization temperature. If a molecular weight regulator is used, the type and amount of the molecular weight regulator may be adjusted, or the monomer may be post-added to the reaction system by propping, or a low molecular weight and a large molecular weight may be separately synthesized. Can be produced by a method such as blending to broaden the molecular weight distribution.

When the unsaturated bonds remaining in the molecular chain of the synthesized polymer are saturated by a hydrogenation reaction, the hydrogenation rate is set to 90 from the viewpoints of light resistance and weather resistance.
% Or more, preferably 95% or more, particularly preferably 99%
Above. The thermoplastic norbornene-based polymer in the present invention has a Tg of 10 from the viewpoint of heat resistance and moldability.
It is desirable that the temperature is 0 ° C or higher, preferably 120 to 200 ° C, and more preferably 130 to 180 ° C.

(2) Method for Reducing Volatile Components The thermoplastic norbornene-based polymer generally contains a volatile component of 0.5% by weight or more in a usual synthesis method. In the molding material of the present invention, the volatile component contained in the thermoplastic norbornene-based polymer is 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. It is desirable. In the present invention, a differential thermogravimeter (TG /
Using DTA200), the loss on heating from 30 ° C. to 350 ° C. is determined, and that amount is defined as the content of the volatile component. When the content of the volatile component is more than the above range, about 250 to 350
When extruded at a temperature of ° C., the volatile components volatilize during molding and foam to become defects inside the molded article, reduce the strength, or appear as streaks on the surface.

As a method for reducing volatile components, for example, in a polymer coagulation method using a poor solvent, there is a method of repeatedly performing coagulation. Direct drying method, 250 ° C or higher, 30To
It is desirable to dry at rr or less using a thin film dryer or an extrusion dryer. Alternatively, the solvent solution of the polymer can be directly dried after being concentrated to several tens% in advance. Of course, it is not limited to these methods. The thermoplastic saturated norbornene-based polymer produced by these methods is substantially amorphous, is excellent in transparency, dimensional stability, heat resistance, water absorption, and hardly recognizes moisture permeability.

(3) Antioxidant In the present invention, the thermoplastic norbornene-based polymer 10
0 to 100 parts by weight of a low volatility antioxidant
When blended at a ratio of 5 parts by weight, decomposition and coloring of the polymer during molding can be effectively prevented.

As the antioxidant, an antioxidant having a vapor pressure at 20 ° C. of 10 ⁻⁵ Pa or less, particularly preferably 10 ⁻⁸ Pa or less, is desirable. An antioxidant having a vapor pressure higher than 10 ⁻⁵ Pa causes problems such as foaming during extrusion molding, and volatilization of the antioxidant from the surface of the molded article when exposed to high temperatures. Examples of the antioxidant that can be used in the present invention include the following, and one or more of these may be used in combination.

Hindered phenol type 2,6-di-t-butyl-4-methylphenol;
6-di-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t
-Butyl-α-methoxy-p-dimethyl-phenol,
2,4-di-t-amylphenol, t-butyl-m-
Cresol, 4-t-butylphenol, styrenated phenol, 3-t-butyl-4-hydroxyanisole, 2,4-dimethyl-6-t-butylphenol, octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 4,4'-bisphenol, 4,4'-
Bis- (2,6-di-t-butylphenol), 2,
2'-methylene-bis- (4-methyl-6-t-butylfinol), 2,2'-methylene-bis- (4-methyl-6-α-methylcyclohexylphenol),
4,4'-methylene-bis- (2-methyl-6-t-butylphenol), 4,4'-methylene-bis- (2,
6-di-t-butylphenol), 1,1'-methylene-bis- (2,6-di-t-butylnaphthol), 4,
4'-butylidene-bis- (2,6-di-t-butyl-
Meta-cresol), 2,2'-thio-bis- (4-methyl-6-t-butylphenol), di-o-cresol sulfide, 2,2'-thio-bis- (2-methyl-
6-t-butylphenol), 4,4'-thio-bis (3-methyl-6-t-butylphenol), 4,4 '
-Thio-bis- (2,3-di-sec-amylphenol), 1,1'-thio-bis- (2-naphthol),
3,5-di-t-butyl-4-hydroxybenzyl ether, 1,6-hexanediol-bis- [3- (3
5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6
-(4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], 2,2-thiobis (4-methyl-6-t-butylphenol), N, N '
-Hexamethylenebis (3,5-di-t-butyl-4-
Hydroxy-hydrocinnamamide), calcium bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate), 1,3,5-trimethyl-2,4,6
-Tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1, 3,5-trimethyl-2,4,6, -tris (3,5-di-t-butyl-4
-Hydroxybenzyl) benzene, tris- (3,5-
Di-tert-butyl-4-hydroxybenzyl) -isocyanurate, pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxygenyl)
Propionate] and the like.

Aminophenols normal butyl-p-aminophenol, normal butyroyl-p-aminophenol, normal pelagonoyl-p-aminophenol, normal lauroyl-p-aminophenol, normal stearoyl-p-aminophenol, , 6-di-t-butyl-α-dimethyl, amino-p-cresol and the like.

Hydroquinone hydroquinone, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, hydroquinone methyl ether, hydroquinone monobenzyl ether and the like.

Phosphite triphosphite, tris (3,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4 '-Biphenylenephosphanite, 2
-Ethylhexyl octyl phosphite and the like.

Others 2-mercaptobenzothiazole zinc salt, dicatechol borate-di-o-tolylguanidine salt, nickel-dimethyldithiocarbamate, nickel-pentamethylene dithiocarbanate, mercaptobenzimidazole, 2-mercaptobenzimidazole zinc salt etc.

(4) Other Ingredients The thermoplastic norbornene-based polymer of the present invention may contain, as an additive other than an antioxidant, various antistatic agents, lubricants, and surfactants as long as the object of the present invention is not impaired. And an ultraviolet absorber. Further, when used for applications other than optical materials, if necessary, additives such as fillers such as glass fibers, dyes, and pigments may be added.

(5) Pelletization and Pre-Drying The plastic material is usually supplied as pellets having a diameter of about 1 to 7 mm and a length of about 4 to 8 mm, and is formed into a desired shape by an extrusion molding method or an injection molding method. Processed. By the way, in general, the polymer after synthesis removes the solvent used at the time of synthesis by a coagulation method or a direct drying method, and the above-mentioned various additives are added to the necessary volume, and in the case of a thermoplastic norbornene-based polymer, The mixture is extruded into a strand having a predetermined diameter in a molten state at a temperature of about 230 ° C. or higher, and then cut into a desired length by a suitable strand cutter to form a pellet.

In the case of ordinary plastic materials, the pellets are formed as they are. For example, in the case of resins having high hygroscopicity or easily decomposing, such as polycarbonate resin, acrylic resin and polyamide resin, moisture is absorbed during storage of the pellets. If it is molded as it is,
Since foaming is severe and defects such as large streaks occur on the surface of the molded product, it is common practice to pre-dry for several hours below the glass transition temperature of the resin before using it and then mold it. I have.

However, since the thermoplastic norbornene-based polymer has low hygroscopicity and does not contain a component that decomposes during storage, conventionally, it is considered that this preliminary drying is unnecessary, and the thermoplastic norbornene-based polymer is molded without preliminary drying. Was. Actually, even if pre-drying is attempted, almost no volatile components are detected.
However, surprisingly, when the pellets of the thermoplastic norbornene-based polymer were pre-dried, fine voids and crack-like defects that could not be seen visually without pre-drying occurred in the molded article, whereas these It has been found that a microvoid-free molded article can be obtained.

The molded article thus obtained is free from microvoids even after molding, and is subjected to, for example, a durability test at a high temperature and high humidity of 70 ° C. or more and a relative humidity of 80% or more and 20 hours or more. No microvoids occur. It was also confirmed that this drying treatment was effective for injection molding.

As conditions for the pre-drying, it is effective that the temperature is high and the drying time is long. However, if the temperature is higher than the glass transition temperature of the resin, the pellets are thermally fused to each other, making it difficult to use. And (Tg-30) to (Tg-5) ° C.
It is particularly preferable to perform the treatment at (Tg-20) to (Tg-5) ° C., preferably for 1 hour or more, particularly preferably for 2 hours or more.

Drying is effective whether it is vacuum drying or normal pressure drying in an air or nitrogen atmosphere. The time from the end of the drying treatment to the time of use for molding is not short, but does not need to be particularly short, and the effect is not lost even after several days.

(6) Molding Method Extrusion Molding The thermoplastic norbornene-based polymer of the present invention is particularly suitable for extrusion molding, but is not limited thereto. In extrusion molding, using a melt extruder, a thermoplastic norbornene-based polymer is heated to about 250 to 300 ° C., extruded from a T-type or manifold-type die, and wound up with various rolls to form a sheet or film. be able to. In this case, since the thermoplastic norbornene-based polymer has high heat resistance and high rigidity, if cooled rapidly by a roll, the surface is wavy like a polycarbonate and cannot be formed flat, so that the first and second winding steps are performed. As described above, the cooling roll was used for the molecular weight distribution (Mw / M
According to the value of n), it is appropriate to set the temperature to a relatively high temperature of about 70 to 140 ° C. and to cool it. Further, the sheet-like molded product can be further stretched uniaxially or biaxially to be processed. In addition, there is a process using a calendar roll.

In order to further supplement the strength and gas permeability of the laminated thermoplastic thermoplastic norbornene-based polymer, other olefin-based resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate, and halogens such as polyvinyl chloride and polyvinylidene chloride. It is possible to perform co-extrusion processing or lamination processing with a fluorinated hydrocarbon resin or the like.

Other Extrusion Molding By extruding a thermoplastic norbornene-based polymer from an appropriate die, it can be extruded into a rod, fiber, or tube. These extruded products can be stretched at a temperature equal to or lower than the glass transition temperature and processed into a thinner rod or tube.

Crosslinking In order to increase the strength, crosslinking can be performed by heating or irradiation with radiation such as ultraviolet rays or electron beams. In this case, it is effective to use an appropriate crosslinking agent. Known crosslinking agents can be used, for example, monomers having a plurality of vinyl groups such as divinylbenzene; polyfunctional acrylates such as diallyl phthalate, ethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate; triallyl isocyanurate and the like Isocyanurates; and polymers having a plurality of unsaturated bonds such as liquid polybutadiene.

Other Molding Methods The thermoplastic norbornene-based polymer of the present invention can be molded by the following molding method other than melt extrusion molding. It can be formed into a sheet by hot pressing. In addition, thermoplastic norbornene-based polymer benzene, toluene,
Aromatic hydrocarbon solvents such as xylene, cyclohexane,
Dissolve in alicyclic hydrocarbon solvents such as methylcyclohexane and decalin, and halogen solvents such as chloroform and monochlorobenzene, and cast these solutions on a flat plate or on a roll to form a film. It is possible. For a polymer having a relatively large molecular weight, it can be spun from the solvent solution. A polymer having a relatively small molecular weight can be subjected to ordinary injection molding, and a general thermoplastic resin processing method such as rotational molding can be applied.

(7) Applications Optical Materials and Conductive Composite Materials The thermoplastic norbornene-based polymer (molding material) of the present invention is amorphous, has excellent transparency, and has small birefringence. , As various optical materials,
Suitable as a substrate material for optical recording media.

The molded article obtained from the thermoplastic norbornene-based polymer of the present invention may be formed on a surface thereof by a thin film forming method such as vacuum evaporation or sputtering, by using a metal, a metal oxide, a metal nitride, a metal sulfide, or a metal halide. Compounds,
Depending on the purpose, a single-layer or multilayer film can be formed.
At this time, the molded product obtained by the present invention may be exposed to a considerably high temperature in a vacuum, but the molded product obtained by the present invention has a small amount of volatile components and a small amount of outgas. Yes, and "swelling" on the surface
It is possible to form a flat film without generation of the like.

A recording medium can be manufactured by providing an optically recordable and / or readable recording thin film on a transparent substrate. As a recording material for forming a recording thin film (recording layer), any known rare earth-transition metallurgy amorphous alloy may be used. For example, a Tb-Fe-based alloy (Japanese Patent Publication No.
No. 20691), a Dy-Fe alloy (JP-B-57-20)
No. 692), Cd-Tb-Fe-based alloys (JP-A-56-1)
No. 26907), Cd-Tb-Dy-Fe-based alloys (JP-A-57-94948), and Cd-Co-based alloys (JP-A-5-94948).
No. 4-121719) and Tb-Fe-Co type. These rare earth-transition metal amorphous layers are preferably formed by a thin film forming method such as vapor deposition, sputtering, or ion plating. The thickness of this amorphous layer is generally between 500 and 1500 degrees. Further, a phase-change type recording material may be used as the recording layer.
e system, Sb-Te system, In-Sb system, Ge-Sb-Te
System, In-Sb-Te system and the like. These phase-change recording materials are preferably formed by a method such as vapor deposition, sputtering, or ion plating. The thickness of this amorphous layer is generally between 500 and 2000 °.

Organic dye-based recording materials can also be used, for example, methine / polymethine-based materials (dianines: indolonine type, thiazole type, etc., croconiums, squaryliums) (JP-A-58-113696); quinones; Naphthoquinones and anthraquinones (Japanese Unexamined Patent Publication No.
199291, JP-A-58-112793); phthalocyanines (metal phthalocyanines) (JP-A-61-112793)
235188, JP-A-59-11292); dithiol-based (dithiol metal complexes) (JP-A-57-1109)
No. 0); other, tetrahydrocholines, dioxane,
Dithiazines, thiapyryliums, porphyrins (JP-A-58-1970088, JP-A-61-235188)
And JP-A-59-78891). The film thickness of this organic dye-based recording material after film formation is generally 500 to 5000 °.

Further, for example, Te-CS ₂ , Pb-Te
_{-Se, Te-C, TeO 2} , Sb-Se, Bl-Te
Etc., or a write-once type recording card using a shape change such as bubble formation. Further, gold, platinum, aluminum or the like can be used as the reflection film.

In the optical recording medium, a surface protective layer may be provided on the surface, or a protective layer, a reflective layer, and a dielectric layer may be provided between the recording layer and the substrate made of the polymer of the present invention. Examples of layer forming materials such as these protective layers include CdS and ZnS.
e, SiO ₂ , Si, Si ₃ N, Si ₃ N ₄ , AlN, Ti
Examples thereof include inorganic substances such as O ₂ , TaO ₂ , TaO ₂ , and MgF ₂ , and organic substances such as an ultraviolet curable resin. Further, in the case of an optical card or the like, other materials may be directly bonded and used. In this case, in addition to a normal adhesive such as a solvent, a hot melt, a UV-curable adhesive, a high-frequency wave, an ultrasonic wave, or the like. An adhesive method is used.

Other Applications The thermoplastic norbornene-based polymer and the molding material of the present invention are a plastic optical fiber for short-distance information transmission including automobile and medical use and its connectors; a lens for picking up information; Lenses for projectors, spectacle lenses, sports goggles, plastic lenses such as head lamps and tail lamp lenses and covers for automobiles, etc .; screens and polarizing films, such as touch electrodes and liquid crystal substrates provided with a transparent conductive film on the surface;
Transparent plate for information display such as anti-glare filter for CRT; Insulation film and moisture-proof coating for electronic devices etc., taking advantage of moisture resistance and insulation; syringes, pipettes, chemical containers, containers and films for optical analysis, etc. Medical equipment; windshields for automobiles, windshields for motorcycles, window materials for aircraft, window materials for housing, transparent shutters, window materials such as lighting equipment and mirrors; beverage containers such as juice, liquor, carbonated beverages, food containers; A film, an appropriate filler, a dye, a pigment and the like are added and dissolved in a solvent to be useful for applications such as a moisture-resistant paint.

The composite material having a conductive film formed on its surface can be used for a touch electrode, a liquid crystal substrate, etc. by providing a transparent film, and a high frequency circuit board, a film for a capacitor, etc. It is also useful as a device material. The optical recording medium having a recording thin film on its surface is useful as a reflective or dye-based information recording medium such as an optical card, an optical floppy (registered trademark), an optical tape, and various memories for computers.

[0059]

The present invention will be specifically described below with reference to Synthesis Examples and Examples. In the following examples, parts and percentages are by weight unless otherwise specified.

[Synthesis Example 1] (Synthesis of ring-opening polymer) Under a nitrogen atmosphere, 90 parts of dehydrated toluene, 0.5 part of triethylaluminum, 1.4 parts of triethylamine, and 1- 0.08 parts of hexene was added. Ethyl tetracyclododecene (ETD) 30
And 0.17 part of titanium tetrachloride were continuously added to the reaction system over 1 hour to carry out a polymerization reaction. ETD
After adding the total amount of and titanium tetrachloride, the reaction was carried out for 1 hour. Next, the reaction was stopped by adding a mixed solution of isopropyl alcohol / aqueous ammonia (0.5 parts / 0.5 parts), and the reaction product was poured into 500 parts of isopropyl alcohol to coagulate. The coagulated polymer is cured at 60 ° C for 10
After vacuum drying for 2 hours, 25.5 parts of a ring-opened polymer was obtained.

(Hydrogenation reaction) The obtained ring-opened polymer was dissolved in 200 parts of cyclohexane, and a palladium / carbon catalyst (supporting amount: 5) was placed in a 200-liter autoclave.
%), Hydrogen pressure 70 kg / cm ² , temperature 1
The hydrogenation reaction was performed at 40 ° C. for 4 hours.

(Post-treatment) After the hydrogenation catalyst was removed by filtration, the reaction solution was poured into 600 parts of isopropyl alcohol to coagulate.

The obtained hydrogenated product was vacuum-dried at 60 ° C. for 10 hours, and then redissolved in cyclohexane to obtain 10%.
% Solution. Poured into 600 parts of isopropyl alcohol and coagulated again. After the drying and coagulation were performed once again in the same manner as described above, each of the obtained hydrogenated products was vacuum-dried at 90 ° C. for 48 hours to obtain 22.6 parts of a hydrogenated product.
The yield was 75%.

(Characteristics of Polymer) The hydrogenation rate of the obtained hydrogenated product was determined by ¹ H-NMR spectrum analysis.
More than 99%. In addition, high performance liquid chromatography (HLC) analysis using toluene as a solvent (TSKgelG5000H by HLC802L manufactured by Tosoh Corporation).
-G4000H as a column, temperature 38 ° C, flow rate 1.
As a result of measuring the molecular weight (in terms of polystyrene) at 0 ml / min), the number average molecular weight (Mn) was 7.0 × 10 ⁴ , the weight average molecular weight (Mw) was 17.5 × 10 ⁴ , and the molecular weight distribution (Mw / Mn). 2.5. The glass transition temperature (Tg) was measured by DSC analysis, and the volatile content was measured by thermogravimetric analysis (TGA) as a loss on heating from 30 ° C. to 350 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere. Tg was 142 ° C. and volatile content was 0.08%.

(Pelletization) To 100 parts of the obtained thermoplastic norbornene-based polymer, as an antioxidant,
1,3,5-trimethyl-2,4,6-tris (3,5
-Tert-butyl-4-hydroxybenzyl) benzene (trade name Irganox 133, manufactured by Ciba Geigy)
0, and a vapor pressure of 1.3 × 10 ⁻¹² Pa), and after mixing with a Henschel mixer, pellets were formed at 230 ° C. using an extruder.

(Molding) Thermoplastic 30 mm
Using a φ extruder, the resin was heated to 280 ° C. and heated to melt and extruded from a T-die to obtain a film having a width of 20 cm and a thickness of 100 μm. At this time, the temperature of the take-up roll was 130 ° C. in the first stage and 121 ° C. in the second stage.

When the film was visually observed, there was no streak on the surface of the film, no foaming was observed inside, and a transparent and defect-free film was obtained. When the tensile strength was measured, it was 900 kg / cm ² . Further, when this film was observed by rotating it while sandwiching it between two polarizing plates whose polarization axes were perpendicular to each other, there was no bright portion and no birefringence. Further, the film was heated in an air oven at 110 ° C. for 48 hours, but there was no coloring.

[Reference Example 1] The following experiment was conducted to check the effect of preliminary drying. The pellets obtained in Synthesis Example 1 were directly extruded under the same conditions as in Synthesis Example 1 to obtain a sheet-shaped molded product having a thickness of 500 μm. The tensile strength of the sheet was 900 kg / cm ² . When this molded product was visually observed, there were no transparent and large defects. However, when the microvoids were counted by observing 10 visual fields with a 400 × optical microscope, microvoids having a size of about 5 μm were observed. In addition, this sheet
After being kept in a thermo-hygrostat at 90 ° C. and a relative humidity of 90% for 1000 hours, it was taken out and visually observed. As a result, a large number of small crack-like defects were observed.

Similarly, Table 1 shows the test results for the sheet obtained by subjecting the pellets of Synthesis Example 1 to pre-drying by changing various drying conditions with a hot air drier and then forming and processing the sheets together with the above results.

[0070]

[Table 1]

(Note) The evaluation criteria for microscopic observation are as follows. A: No microvoids, B: Number of microvoids 2 or less, C: Number of microvoids 4 or less, D: Number of microvoids 5 or more.

[0072]

According to the present invention, a norbornene-based polymer having excellent heat resistance, water resistance, strength and the like is co-extruded with another resin to thereby obtain the strength and gas permeability of the norbornene-based polymer. Is provided. Further, according to the present invention, it is made of a thermoplastic norbornene-based polymer and another resin, which is excellent in heat resistance, water resistance, strength, etc., and can provide a molded product having no defects such as microvoids, foams, and streaks. A laminate is provided. The laminate of the present invention is suitable for the various uses described above, for example, as a packaging film or container.

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Claims (6)

[Claims] (A) a thermoplastic norbornene-based polymer, (B) another olefin-based resin, a polyester resin,
And a laminate comprising at least one resin selected from the group consisting of halogenated hydrocarbon resins. 2. The laminate according to claim 1, which is obtained by coextrusion or lamination. 3. The laminate according to claim 2, which is obtained by co-extrusion when extruding a norbornene-based polymer into a sheet or film. 4. A method in which a norbornene-based polymer is extruded into a sheet-like molded product, and is obtained by co-extrusion during the extrusion in the case of stretching in a uniaxial or biaxial direction. 3. The laminate according to 2. 5. The laminate according to claim 1, which is a packaging film or a container. 6. The laminate according to claim 1, wherein the thermoplastic norbornene-based polymer is a thermoplastic saturated norbornene-based polymer.