JP2006124657A - Injection molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a molding being a thin injection molding which has ≤500μm thickness and in which the area of the principal plane of the molding is a specific value or above, comprising a thermoplastic saturated norbornene-based resin which has excellent molding processability during molding, causes no crack during demolding, has excellent transparency, mechanical strength, transfer properties and heat resistance of an obtained molding. <P>SOLUTION: The molding has ≤500μm thickness t (μm), the surface S (μm<SP>2</SP>) of the principal plane of the molding represented by the numerical expression of formula (I) S≥2×10<SP>6</SP>×t. The molding is obtained by injection molding a thermoplastic saturated norbornene-based resin having (1) 5-16g/10 minutes melt mass flow rate (MFR) at 230°C at 2.16kg load, (2) ≥110°C glass transition temperature (X) and (3) a weight-average molecular weight (Y) in the range represented by the numerical expression of formula (II) Y≥20×(X-100)<SP>2</SP>+10,000. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thin injection molded article made of a thermoplastic saturated norbornene resin useful as an optical member such as a light guide plate.

  Conventionally, an optical molded body such as a light guide plate and an optical lens is manufactured by injection molding a thermoplastic resin. In addition, as a thermoplastic resin for producing such an optical molded body, a norbornene-based addition polymer or a norbornene-based ring-opening polymer hydride that is excellent in transparency, molding processability, mechanical strength, and the like is used. ing.

  Generally, in order to obtain a good molded article, it is considered important to use a resin excellent in melt fluidity at the time of molding. If the melt flowability of the thermoplastic resin is poor, it will not be possible to obtain a good molded product even if the processing conditions (for example, temperature, pressure, etc.) at the time of molding are changed, or the shape of the molded product obtained will be There may be inconveniences such as restrictions.

  For example, Patent Document 1 discloses an injection-molded article made of a thermoplastic saturated norbornene resin having a specific number average molecular weight, having a thin portion with a thickness of 700 μm or less over 25 mm along the flow direction from the gate. Although proposed, the thermoplastic saturated norbornene-based resin used has poor fluidity and poor transferability, so that a good molded product may not be obtained.

  As a conventional technique for producing a molded body using a resin having excellent melt fluidity at the time of molding, for example, Patent Document 2 discloses high transparency, excellent moldability, and mechanical strength and heat resistance. A norbornene-based addition polymer having a melt mass flow rate (hereinafter sometimes referred to as “MFR”) of 60 to 200 g / 10 min at 280 ° C. and a load of 2.16 kg is disclosed as a polymer having both. Patent Document 3 discloses that a polymer having high transparency, excellent moldability, and having both mechanical strength and heat resistance has an MFR of 50 to 300 g / 10 min at 280 ° C. and a load of 2.16 kg. Certain norbornene-based ring-opening polymer hydrides have been disclosed.

JP-A-5-47034 JP 2000-169558 A JP 2000-219725 A

  However, in the case of producing a thin molded body having a thickness of 500 μm or less and an area of the main surface of the molded body having a specific value or more by an injection molding method, the norbornene-based addition polymer used as described in the above document If only the MFR of the hydride of norbornene-based ring-opening polymer is adjusted, the resulting injection-molded product is inferior in heat resistance, or cracking may occur at the time of mold release even if it has excellent heat resistance. I understood it.

  The present invention has been made in view of such problems of the prior art, and is a thin injection-molded body having a thickness of 500 μm or less and an area of the main surface of the molded body of a specific value or more, To provide a molded article made of a thermoplastic saturated norbornene-based resin that is excellent in molding processability, does not cause cracking at the time of mold release, and has excellent transparency, mechanical strength, transferability and heat resistance. Let it be an issue.

  In order to solve the above-mentioned problems, the present inventors diligently studied a thin molded body obtained by injection molding a thermoplastic saturated norbornene resin.

  In general, in the case of producing an injection-molded article using a thermoplastic resin, it is necessary to increase the MFR value (that is, increase the fluidity) in order to ensure high transferability. The molecular weight of the resin must be lowered. However, if the molecular weight of the thermoplastic resin used is too small, the bending strength of the injection-molded product is insufficient, and the molded product is likely to be cracked at the time of mold release. Further, if the glass transition temperature (X) of the thermoplastic resin is constant, the weight average molecular weight (Y) and MFR are in an inversely proportional relationship, and if the MFR is the same, the lower the glass transition temperature (X) is. The weight average molecular weight (Y) increases. Therefore, in order to obtain an injection molded article having excellent transferability and a certain bending strength by using a thermoplastic resin having excellent fluidity, the glass transition temperature (X) is lowered and the molecular weight is increased. do it. On the other hand, however, if the glass transition temperature (X) is too low, an injection molded article having excellent heat resistance cannot be obtained.

  In consideration of the above matters, the inventors of the present invention have a transparency and molding processability when manufacturing a thin molded body having a thickness of 500 μm or less and an area of the main surface of the molded body of a specific value or more by an injection molding method. And a thermoplastic saturated norbornene resin excellent in mechanical strength, etc., having a specific melt mass flow rate and a glass transition temperature higher than a specific temperature, and having a specific relationship between the weight average molecular weight and the glass transition temperature. By using this, we obtained the knowledge that a thin injection-molded body having excellent transferability, heat resistance and strength characteristics (no cracking at the time of mold release and cracking in the stress test) can be obtained. The present invention has been completed based on the findings.

Thus, according to the present invention, the thickness t (μm) is 500 μm or less, and the area S (μm ² ) of the main surface of the molded body is

A molded body which is
(1) The melt mass flow rate (MFR) at 230 ° C. and a load of 2.16 kg is in the range of 5 to 16 g / 10 minutes,
(2) The glass transition temperature (X) is 110 ° C. or higher, and
(3) The weight average molecular weight (Y) is

A molded body obtained by injection molding a thermoplastic saturated norbornene resin in the range of is provided.
In the molded article of the present invention, the thermoplastic saturated norbornene resin is preferably a hydride of a norbornene ring-opening polymer, and preferably has a bending strength of 300 kgf / cm ² or more.
Moreover, it is preferable that the molded object of this invention is a light-guide plate.

  According to the present invention, a thin injection molded body having a thickness of 500 μm or less and an area of the main surface of the molded body is not less than a specific value, excellent in molding processability at the time of molding, and cracking at the time of mold release There is provided a molded article made of a thermoplastic saturated norbornene resin that is excellent in transparency, mechanical strength, transferability and heat resistance of the obtained molded article.

Hereinafter, the molded article of the present invention will be described in detail.
The present invention is a thin molded body obtained by injection molding of a thermoplastic resin.
In the molded article of the present invention, a thermoplastic saturated norbornene resin excellent in transparency, molding processability and mechanical strength is used as the thermoplastic resin.

(1) Thermoplastic saturated norbornene resin In the present invention, the thermoplastic saturated norbornene resin means (A) a hydride of a ring-opening polymer of a norbornene monomer, a norbornene monomer, and a norbornene monomer. Hydrides of ring-opening copolymers with other monomers copolymerizable with the polymers (hereinafter, these may be collectively referred to as "hydrides of norbornene-based ring-opening polymers"), and (B) norbornene Addition-polymerization of resins based on addition monomers and addition copolymers of norbornene monomers and other monomers that can be addition copolymerized with norbornene monomers (hereinafter referred to as “norbornene-based monomers”) Sometimes referred to as an addition polymer).

  In the present invention, the norbornene monomer is a compound having a norbornene structure represented by the following formula (1).

(A) Hydride of norbornene-based ring-opening polymer The hydride of norbornene-based ring-opening polymer used in the present invention is a norbornene-based monomer, or norbornene-based monomer, and norbornene-based monomer and ring-opening. A norbornene-based ring-opening polymer obtained by ring-opening polymerization with a copolymerizable monomer can be obtained by hydrogenation.

As the norbornene-based monomer, bicyclo [2.2.1] hept-2-ene (common name: norbornene), 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-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-methyl Octanate, 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 [ 2.1] hept-2-ene, 5-hydroxy-isopropyl-bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene, 5,6-di Carboxy-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 [4.3.0.1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 ^{2 , 5]} dec-3-ene, tricyclo [4.4. .1 ^2,5] undec-3,7-diene, tricyclo [4.4.0.1 ^2,5] undec-3,8-diene, tricyclo [4.4.0.1 ^2,5] undec - 3-ene, tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7] trideca -2,4,6,11- tetraene (common name: 1,4-methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11,14} . Norbornene having no norbornane structure such as 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (common name: 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene) System monomer; tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-vinyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-propenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-hydroxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-carboxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 17,10] dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.0.1 ^3,6. 1 ^10,13 . 0 ^2,7 ] norbornene monomers having one or more norbornane structures such as pentadeca-4,11-diene.
These norbornene monomers can be used alone or in combination of two or more.

The other monomer capable of ring-opening copolymerization with the norbornene monomer is not particularly limited as long as it can be ring-opening copolymerized with the norbornene monomer. For example, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano Cycloolefin such as -1H-indene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; Can do.
Other monomers copolymerizable with these norbornene monomers can be used alone or in combination of two or more.

  The proportion of the repeating unit derived from the norbornene monomer in the hydride of the norbornene ring-opening polymer is usually 50 to 100% by weight, preferably 70 to 100% by weight, more preferably 90 to 100% by weight, particularly preferably. Is 100% by weight. By setting the ratio of the repeating unit derived from the norbornene-based monomer within this range, the mechanical strength of the obtained molded body is improved.

  The ring-opening polymerization of the norbornene monomer or the monomer copolymerizable with the norbornene monomer can be performed in the presence of at least a metathesis catalyst and a molecular weight regulator.

  The metathesis catalyst to be used is not particularly limited as long as it can ring-open polymerization a norbornene monomer. The metathesis catalyst is a complex formed by bonding a plurality of ions, atoms, polyatomic ions and / or compounds with a transition metal atom as a central atom.

  As transition metal atoms, atoms of Group 4, Group 5, Group 6 and Group 8 (long-period periodic table, the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 4 atom include titanium, examples of the Group 5 atom include tantalum, and examples of the Group 6 atom include molybdenum and tungsten. Examples of Group 8 atoms include ruthenium and osmium.

  Metathesis catalysts centered on Group 6 tungsten and molybdenum include metal halides such as tungsten hexachloride; metal oxyhalides such as tungsten chloroxide; metal oxides such as tungsten oxide; and tridodecyl ammonium molybdate And organic metal acid ammonium salts such as tri (tridecyl) ammonium molybdate can be used.

  The amount of these metathesis catalysts used is usually in the range of about 0.001 to 50 mmol, preferably 0.002 to 20 mmol, with respect to 1 mol of the norbornene monomer. When these metathesis catalysts are used, it is preferable to use them together with an activator (cocatalyst) for the purpose of controlling the polymerization activity. The activator is an organoaluminum compound or an organotin compound. The activator is preferably in the range of 1 to 10 (molar ratio) with respect to the metathesis catalyst component.

  Further, as the metathesis catalyst, a metal carbene complex having a group 4, 5, 6, or 8 metal atom as a central atom can also be used. A metal carbene complex has a structure (M = C) in which a carbene compound is bonded to a central metal atom and a metal atom (M) and a carbene carbon are directly bonded to each other. The carbene compound is a general term for compounds having a carbene carbon, that is, a methylene free radical. Among the ruthenium carbene complexes, a ruthenium carbene complex in which at least two carbene carbons are bonded to a ruthenium metal atom and a group containing a hetero atom is bonded to at least one of the carbene carbons is particularly preferable.

  Here, the hetero atom means an atom of Groups 15 and 16 of the periodic table, and specifically includes N, O, P, S, As, and Se atoms. Among these, from the viewpoint of obtaining a stable carbene compound, N, O, P, S atoms and the like are preferable, and N atoms are particularly preferable.

  Examples of the ruthenium carbene complex include benzylidene (1,3-dimesitylimidazolidine-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3- Methyl-2-butene-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-octahydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-Phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexene) Sylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazol-5-ylidene) ruthenium dichloride, Heteroatom-containing carbene such as 1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesitylimidazolidine-2-ylidene) pyridine ruthenium dichloride A ruthenium carbene complex in which a compound and a neutral electron donating compound are bound;

  Ruthenium in which two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride are bonded. Carbene complex; and the like.

  The amount of the metathesis catalyst used is appropriately selected depending on the polymerization conditions, but is usually 1/10 to 1 / 1,000,000, preferably 1/100 to 1 / 500,000, in a molar ratio to the total monomers. More preferably, it is in the range of 1/1000 to 1 / 200,000. When it is within this range, the molecular weight can be easily controlled and the MFR can be easily controlled.

  Moreover, when performing metathesis polymerization, a co-catalyst can be used with the said metathesis catalyst. Examples of the cocatalyst to be used include an organoaluminum compound and an organotin compound, and an organoaluminum compound is preferable.

Specific examples of the organoaluminum compound include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, and triisobutylaluminum, and alkylhalidealuminum such as diethylaluminum chloride and ethylaluminum dichloride. Are preferably triethylaluminum, triisobutylaluminum and diethylaluminum chloride.
These promoters can be used alone or in combination of two or more.

  When the amount of the cocatalyst used is usually 0.01 to 30 mol, preferably 0.1 to 20 mol, more preferably 1 to 10 mol, per mol of the metathesis catalyst, generation of a gel or a high molecular weight component occurs. It is preferable because it has a low polymerization activity and can easily control the molecular weight. In the combination of the metathesis catalyst and the cocatalyst, a combination of a tungsten (W) compound and an organoaluminum compound is particularly preferable.

  As the molecular weight regulator, chain monoolefins and chain conjugated dienes are usually used. Examples thereof include 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-dodecene and 1,4-hexadiene. The amount of the molecular weight regulator used is appropriately selected depending on the polymerization conditions, but is usually 1/10 to 1/500, preferably 1/25 to 1/250, more preferably 1 in terms of molar ratio to the total monomers. / 50 to 1/200. When in this range, as will be described later, the molecular weight can be easily controlled and the MFR can be easily controlled.

  The polymerization reaction is usually performed in a solvent. Examples of the solvent used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic chain hydrocarbons such as n-pentane, n-hexane and n-heptane; aliphatics such as cyclopentane, cyclohexane and cyclooctane. Cyclic hydrocarbons; and the like, preferably toluene, cyclohexane, cyclooctane and the like, and more preferably toluene, cyclohexane. These solvents can be used alone or in combination of two or more. The usage-amount of a solvent is 10-1000 weight part normally per 100 weight part of monomers, Preferably it is the range of 50-700 weight part, More preferably, it is the range of 100-500 weight part.

The polymerization temperature is usually in the range of 0 to 150 ° C, preferably 10 to 100 ° C, more preferably 20 to 80 ° C. When it is within this range, the generation of low molecular weight components and the prevention of the formation of gels and high molecular weight components can be performed in a well-balanced manner. The polymerization time is usually in the range of 30 minutes to 10 hours, preferably 1 to 7 hours, more preferably 2 to 5 hours.
After completion of the polymerization reaction, the norbornene-based ring-opening polymer can be isolated from the reaction mixture according to a conventional method.

  Next, the main chain carbon-carbon double bond of the obtained norbornene-based ring-opening polymer is hydrogenated to obtain a hydride of the norbornene-based ring-opening polymer. In addition, a hydrogenation catalyst can be added to the said ring-opening polymerization reaction liquid, and a hydrogenation reaction can also be performed continuously.

  The hydrogenation catalyst to be used is not particularly limited as long as it is generally used for hydrogenation of olefin compounds and aromatic compounds, and a heterogeneous catalyst or a homogeneous catalyst is usually used.

  Examples of the heterogeneous catalyst include, for example, nickel, palladium, platinum, or a solid catalyst supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide using these metals, for example, nickel / silica, nickel. / Diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina and the like.

Examples of the homogeneous catalyst include a catalyst comprising a combination of a transition metal compound and an alkylaluminum compound or alkyllithium, such as cobalt acetate / triethylaluminum, cobalt acetate / triisobutylaluminum, nickel acetate / triethylaluminum, nickel acetate / triisobutyl. Examples of the catalyst include a combination of aluminum, nickel acetylacetonate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene chloride / n-butyllithium, zirconocene chloride / n-butyllithium, and the like.
These hydrogenation catalysts can be used alone or in combination of two or more.

  The amount of the hydrogenation catalyst used is usually in the range of 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight per 100 parts by weight of the norbornene ring-opening polymer. . The hydrogenation reaction is usually carried out at a temperature range of 0 to 250 ° C. and a reaction time of 1 to 20 hours under a hydrogen pressure of 0.1 to 20 MPa.

  The proportion of hydrogenation is usually 50% or more, preferably 70% or more, more preferably 90% or more of the unsaturated bonds in the norbornene-based ring-opening polymer to be hydrogenated.

  When a heterogeneous catalyst is used, the norbornene-based ring-opening polymer hydride used in the present invention is filtered after the hydrogenation reaction to remove the hydrogenation catalyst, followed by a coagulation drying method or a thin film dryer. It can be isolated by a direct drying method using The norbornene-based ring-opening polymer hydride is usually obtained in the form of powder or pellets. When a homogeneous catalyst is used as the hydrogenation catalyst, alcohol or water is added after the hydrogenation reaction to deactivate the catalyst, insolubilized in a solvent, and then filtered to remove the catalyst.

(B) Norbornene-based addition polymer The norbornene-based monomer used for the norbornene-based addition polymer includes the same norbornene-based monomers listed in the section of the norbornene-based ring-opening polymer in (A) above. Can be mentioned.

  Examples of other monomers that can be addition copolymerized with a norbornene monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 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 Ethylene having 2 to 20 carbon atoms such as -1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, or the like; α-olefin; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl)- Cyclocyclones such as cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl- Non-conjugated dienes such as 1,4-hexadiene and 1,7-octadiene; and the like. These norbornene monomers and other monomers capable of addition copolymerization with norbornene monomers can be used alone or in combination of two or more.

  The content of the repeating bond unit derived from the norbornene-based monomer in the norbornene-based addition polymer is usually 10 to 100 mol%, preferably 15 to 90 mol%, more preferably 20 to 80 mol%, and particularly preferably 25. When it is ˜70 mol%, the mechanical strength, transparency, and heat resistance are highly balanced and suitable.

  The norbornene-based addition polymer is one or more of the above norbornene-based monomers, or a norbornene-based monomer and another addition-copolymerizable monomer in a hydrocarbon solvent in the presence of an addition polymerization catalyst. Can be obtained by polymerization.

  Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic chain hydrocarbons such as n-pentane, n-hexane, and n-heptane; cyclopentane, cyclohexane, cyclooctane, and the like. Aliphatic cyclic hydrocarbons; and the like. Among these, aromatic hydrocarbons and aliphatic cyclic hydrocarbons are preferable, toluene, cyclohexane and cyclooctane are more preferable, and toluene and cyclohexane are more preferable. These hydrocarbon solvents can be used alone or in combination of two or more.

  A conventionally known catalyst may be used as the addition polymerization catalyst. For example, those disclosed in JP-A-60-168708, JP-A-612012016, JP-A-2-173112, JP-A-5-9223 and the like can be used. Specific examples include Ziegler catalysts and metallocene catalysts.

Examples of the Ziegler catalyst include a catalyst comprising a vanadium compound and a reducing agent such as an organoaluminum compound. Specifically, it is produced using a catalyst formed from a soluble vanadium compound and an organoaluminum compound. Specific examples of the vanadium compound include VOCl ₃ , VO (OC ₂ H ₅ ) Cl, VO (OC ₂ H ₅ ) ₂ Cl, VO (OiC ₃ H ₇ ) Cl ₂ , VO (On-C ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , and VO (On-C ₄ H ₉ ) ₃ . These vanadium compounds can be used alone or in combination of two or more.

The metallocene catalyst can be usually prepared using a catalyst formed from a metallocene (transition metal component) and an organoaluminum compound.
Examples of the metallocene transition metal include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. Among these, zirconium and hafnium are preferable, and zirconium is more preferable because the catalyst activity can be easily controlled.

  Specific examples of the metallocene having such a transition metal include rac-dimethylsilyl-bis (1-indenyl) zirconium dichloride, rac-dimethylgermyl-bis (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis ( 1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis (1-indenyl) zirconium dichloride, 1-silacyclobutyl-bis (1-indenyl) zirconium dichloride, rac-diphenylsilyl-bis (1-indenyl) hafnium dichloride Rac-phenylmethylsilyl-bis (1-indenyl) hafnium dichloride, rac-diphenylsilyl-bis (1-indenyl) zirconium dichloride, diphenylmethylene (9-fluorenyl) B cyclopentadienyl zirconium dichloride, and isopropylene (9-fluorenyl) cyclopentadienyl zirconium dichloride. Among these, rac-dimethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylmethylsilyl-bis (1-indenyl) zirconium dichloride, rac-phenylvinylsilyl-bis (1-indenyl) zirconium dichloride, rac- Diphenylsilyl-bis (1-indenyl) hafnium dichloride, diphenylmethylene (9-fluorenyl) cyclopentadienylzirconium dichloride, isopropylene (9-fluorenyl) cyclopentadienylzirconium dichloride, and the like are preferable. These metallocenes can be used alone or in combination of two or more.

  Examples of organoaluminum compounds used in Ziegler catalysts or metallocene catalysts include trialkylaluminum, dialkylaluminum alkoxide, alkylaluminum sesquialkoxide, partially alkoxylated alkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, alkylaluminum dihalide. And alkylaluminum partially hydrogenated and partially alkylated and halogenated alkylaluminum. Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide, an alkylaluminum, or a mixture thereof (aluminoxane). These organoaluminum compounds can be used alone or in combination of two or more.

  In the present invention, it is preferable to use a metallocene catalyst in order to efficiently obtain the target MFR norbornene addition polymer.

  Further, it is preferable that the metallocene and the organoaluminum compound are premixed before contacting with the monomer because the polymerization activity is remarkably increased. This premixing is performed by dissolving metallocene in a solution of an organoaluminum compound in a hydrocarbon solvent. The premixing time is usually 10 minutes to 100 hours, preferably 10 minutes to 1 hour. The solution temperature at this time is 0-100 degreeC, Preferably it is 0-70 degreeC.

  The polymerization temperature is usually in the range of 0 to 100 ° C, preferably 0 to 80 ° C, more preferably 0 to 60 ° C. The polymerization pressure is usually from normal pressure to 2 MPa.

The amount of the metallocene catalyst used is usually from 1 to 10 ⁻⁵ mmol / liter, preferably from 10 ⁻¹ to 10 ⁻³ mmol / liter, as a transition metal atom. The amount of the organoaluminum compound used is usually 1 to 10,000, preferably 2 to 1,000, particularly preferably, when expressed as a ratio of aluminum atoms to transition metal atoms in the polymerization reaction system (Al / M). It is in the range of 3-100.

  The addition polymerization reaction can usually be stopped by adding an alcohol compound such as methanol or isopropyl alcohol to the polymerization reaction system. In order to stop the reaction, when the conversion ratio of the norbornene monomer used in the polymerization reaction to the addition polymer is defined as the conversion ratio, the conversion ratio is usually 90% or less, preferably 85% or less. It is desirable to carry out at a time of 80% or less.

  After the reaction is stopped, the catalyst residue is removed, and then the unreacted monomer and hydrocarbon solvent are removed to isolate the norbornene-based addition polymer of the present invention.

  Examples of a method for removing unreacted monomers and hydrocarbon solvents include a solidification method in which solidification is performed by precipitating a resin component by mixing with a poor solvent, and a direct drying method. Among these, the direct drying method does not require the addition of a volatile component such as a poor solvent, and the absolute amount of the volatile component itself can be minimized. Is preferred because it is easy to separate the unreacted monomer.

  The direct drying method includes unreacted monomers other than the polymer components by placing a polymerization reaction solution containing an addition polymer under reduced pressure conditions, preferably from the viewpoint of productivity, preferably under reduced pressure conditions with heating. Volatile components are removed by volatilization and separated from the addition polymer, and the volatilized components removed by volatilization are condensed again by a condenser or other device, and then recovered through a process such as distillation as necessary. Is done. The direct drying method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, an interfacial heat exchange type continuous reactor type dryer, or a high viscosity reactor device.

(2) Melt mass flow rate (MFR)
The molded product of the present invention has an MFR of 5 to 16 g / 10 minutes, preferably 7 to 16 g / 10 minutes, more preferably 8 to 16 g / 10 minutes, and particularly preferably 10 to 16 g / 10 minutes. It is obtained by injection molding a saturated norbornene resin. Thermoplastic saturated norborn resin with MFR in such a range is excellent in melt fluidity at the time of molding, and even if the processing conditions (for example, temperature, pressure, etc.) at the time of molding are changed, fine shape pattern transferability And a molded article having excellent bending strength.

  In the present invention, the MFR of the thermoplastic saturated norbornene resin is a value measured based on JIS-K-6719 at 230 ° C. and a load of 2.16 kg. The fluidity parameter at the time of molding of the resin used is defined by MFR at 230 ° C. close to the molding temperature.

In order to set the MFR of the thermoplastic saturated norbornene resin used in the present invention in such a range, the following may be performed.
For example, when the thermoplastic saturated norbornene resin used is a hydride of a norbornene ring-opening polymer, the norbornene having the desired MFR is changed by changing the amount of the molecular weight regulator added to the polymerization reaction system. A hydride of a ring-opening polymer can be obtained. Among these, it is preferable to add a molecular weight modifier previously diluted with a reaction solvent or the like to the reaction system, or to add a molecular weight modifier weighed using a device with high measurement accuracy. As the accuracy of the weighing, a hydride having an optimum molecular weight is obtained when the required amount of the molecular weight regulator is usually 3% or less, preferably 2% or less, more preferably 1% or less. Control is also easy.

  In addition, when performing ring-opening polymerization, by adding various reaction regulators to the reaction system in addition to the above-described metathesis catalyst, co-catalyst, and molecular weight regulator, the polymerization activity and selectivity of ring-opening polymerization are increased, A hydride of the polymer having the desired specific MFR can be easily obtained.

  The reaction modifier may be at least one polar compound selected from active hydrogen-containing polar compounds such as alcohols and amines; polar compounds not containing active hydrogen such as ethers, esters, ketones, and nitriles. . The active hydrogen-containing polar compound is effective for preventing gel formation and obtaining a polymer having a specific molecular weight, and alcohol is particularly preferable. The polar compound containing no active hydrogen is effective in suppressing the formation of low molecular weight components in the polymer that cause a decrease in mechanical strength. Among them, ethers, esters, and ketones are preferable, and ketones are particularly preferable. More preferred.

Examples of the alcohol include saturated alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, isopentanol, hexanol and cyclohexanol; unsaturated alcohols such as phenol and benzyl alcohol; It is done.
Examples of the ether include dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, ethylene glycol dibutyl ether, triethylene glycol dibutyl ether and the like.
Examples of the ester include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, propyl benzoate, and isopropyl benzoate.
Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl phenyl ketone, and diphenyl ketone.
Examples of the nitrile include acetonitrile, benzonitrile, t-butyronitrile and the like.
These reaction modifiers can be used alone or in combination of two or more.

Among these, it is preferable to combine a polar compound containing active hydrogen and a polar compound having no active hydrogen, and particularly preferable are combinations of alcohol and ketone, alcohol and nitrile, alcohol and ether, and alcohol and ester.
The amount of reaction modifier used is usually in the range of 0.01 to 20 mol, preferably 0.1 to 10 mol, more preferably 1 to 5 mol, per mol of metathesis catalyst.

  Furthermore, when the ring-opening polymerization is performed, the temperature in the reaction system due to the reaction heat at the time of polymerization is higher than the reaction start temperature, preferably 0 ° C. to 30 ° C. higher than the reaction start temperature, more preferably 0 ° C. to 20 ° C. A stable hydride of norbornene-based polymer having the desired MFR can be stably obtained by adjusting the temperature to a higher temperature, more preferably from 0 ° C to 10 ° C, particularly preferably from 0 ° C to 5 ° C. Can do.

  More specifically, at least a part of a metathesis catalyst solution in which a norbornene-based monomer and, if necessary, other monomers copolymerizable with the norbornene-based monomer, and a metathesis catalyst are dissolved in a solvent. Preferred examples include a method of sequentially adding during the reaction, and a method of controlling the balance between reaction heat and heat removal using a heat exchanger or the like.

  In the former method, (i) at least a part of the monomer in the reactor (usually 0.1 to 50% by weight, more preferably 0.2 to 30% by weight of the total amount of monomers used) (Preferably 0.5 to 10% by weight), a molecular weight regulator, a solvent, preferably a cocatalyst, a reaction regulator, and after raising the temperature to a preliminary temperature before starting the reaction, (ii) the entire metathesis catalyst solution, Preferably, a part (usually 1 to 70% by weight of the total amount of catalyst used, more preferably 5 to 60% by weight, more preferably 10 to 50% by weight) is added at a predetermined addition rate to initiate the polymerization reaction, (Iii) Next, while adjusting the temperature in the reaction system within the range of the polymerization temperature, when the remainder of the metathesis catalyst solution occurs in the section (ii), the catalyst solution and the remainder of the monomer are respectively added. It is the method of dripping continuously separately. The time required for dropping is in accordance with the polymerization time. During the ring-opening polymerization reaction, stirring of the reaction system is usually continued. By using this method, it is possible to suitably suppress a rapid temperature increase due to the heat of polymerization reaction.

  The preliminary temperature before the start of the reaction is preferably set to a target polymerization temperature of usually 2 to 15 ° C. or less, preferably 3 to 10 ° C. or less in order to suppress a temperature rise due to polymerization reaction heat. That is, by setting a preliminary temperature somewhat lower than the target polymerization temperature in advance, it is possible to provide a heating means for raising the temperature rise due to the reaction heat at the start of polymerization to the target polymerization temperature as it is. And can prevent an increase in the reaction temperature above the target polymerization temperature. This also suppresses low molecular weight components and high molecular weight components or gel components that are by-produced by the polymerization reaction, that is, particularly in the region where the MFR is high. Since it is possible to control MFR in a coalescence, it is suitable for producing a hydride of a polymer within the MFR range of the present invention.

  In order to suppress a rapid temperature increase due to the heat of polymerization reaction, it is preferable to use a reaction vessel equipped with a heat exchanger having a sufficient heat removal capability. The heat medium for the heat exchanger may be any one of a water medium, an oil medium, an electric heating medium, and a steam medium. However, for a suitable heat removal capability, a water medium and an oil medium are preferable. In the present invention, in order to suitably keep the temperature increase during the ring-opening polymerization from the start of the polymerization within the above-mentioned range, it is more preferable to implement all means for suppressing the polymerization temperature increase due to the reaction heat.

Moreover, when the thermoplastic saturated norbornene-type resin to be used is a norbornene-type addition polymer, what has the target MFR can be obtained as follows.
That is, when the concentration of the addition polymerization catalyst and the norbornene monomer in the reaction system are sufficient to advance the polymerization reaction (that is, from the initial stage to the middle stage of the reaction), the polymerization reaction rate is almost constant. And using the time as a measure for stopping the reaction to some extent (for example, sampling the reaction solution during the polymerization reaction at regular intervals, quantifying the amount of monomer, The time point at which the desired MFR is obtained) is predicted, and the reaction is terminated, whereby an addition polymer having the desired MFR can be obtained.

  In addition, when the addition polymerization catalyst concentration and the norbornene monomer concentration in the reaction system are dilute to proceed the polymerization reaction (that is, at the final stage of the reaction), the target MFR is set to the target time using the time as a guide. It becomes difficult to stop the reaction in anticipation of the given time. Therefore, when an addition polymer having a specific MFR value is selectively obtained as in the present invention, the MFR can be easily controlled by stopping the reaction at the time point within the above conversion rate range. Can be achieved.

(3) Glass transition temperature (X)
The molded article of the present invention is obtained by injection molding a thermoplastic saturated norbornene resin having a glass transition temperature (X) of 110 ° C. or higher, preferably 110 to 200 ° C., more preferably 115 to 180 ° C. . A thermoplastic saturated norbornene resin having a glass transition temperature (X) in such a range is suitable because the heat resistance and molding processability are highly balanced.

  The glass transition temperature (X) depends on the type of repeating unit contained in the thermoplastic saturated norbornene resin used, the weight average molecular weight, the three-dimensional structure, and the like. As a tendency, the glass transition temperature increases as the structure of the norbornene monomer contained in the thermoplastic saturated norbornene resin increases from two rings to three rings and four rings. Moreover, the glass transition temperature becomes higher as the proportion of the repeating unit derived from the norbornene monomer contained in the thermoplastic saturated norbornene resin increases. Since the glass transition temperature varies depending on the type of substituent of the norbornene monomer, a thermoplastic saturated norbornene resin having a desired glass transition temperature (X) can be obtained by adjusting the above items. .

(4) Weight average molecular weight (Y)
The molded product of the present invention has a weight average molecular weight (Y) of

It is obtained by injection molding a thermoplastic saturated norbornene resin.
In addition to excellent transparency and molding processability by using thermoplastic saturated norbornene resin that has a specific relationship of weight average molecular weight (Y) to glass transition temperature (X) as thermoplastic resin for injection molding Thus, it is possible to obtain a thin injection-molded body having excellent transferability and strength characteristics (no cracking at the time of release and cracking in the stress test).

  As a method for setting the weight average molecular weight (Y) of the thermoplastic saturated norbornene-based resin to a predetermined value, when the norbornene-based monomer is subjected to ring-opening polymerization to produce a norbornene-based ring-opening polymer, the reaction temperature, By controlling reaction time etc., the method etc. which obtain the norbornene-type ring-opening polymer which has a desired weight average molecular weight semiempirically are mentioned.

(5) Injection molding method The molded body of the present invention is manufactured by injection molding a molding material. The injection molding method is preferable because it is excellent in moldability and productivity.

  The molding material used is one or more of the above-mentioned thermoplastic saturated norbornene resins. In the present invention, if necessary, other resins, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, fluorescence enhancing agents. Other compounding agents such as whitening agents can be used alone or in admixture of two or more, and the compounding amount can be appropriately selected within a range not impairing the object of the present invention.

  The method of blending the compounding agent with the thermoplastic saturated norbornene resin is not particularly limited as long as these compounding agents are sufficiently dispersed in the thermoplastic saturated norbornene resin. For example, a method of kneading the above components in a state where the resin is melted in a mixer, a uniaxial kneader, a biaxial kneader, or the like, or dissolving and dispersing in an appropriate solvent and then coagulating, casting, or directly drying the solvent There is a method to remove. When a biaxial kneader is used, after kneading, it is usually extruded in a rod shape in a molten state, cut into an appropriate length with a strand cutter, and pelletized in many cases. In the case of kneading, generally, a sufficient share is applied at a resin temperature in a region 20 to 150 ° C. higher than the glass transition temperature of the resin. If the resin temperature is low, the viscosity is high and kneading is difficult, and if it is too high, the resin and the compounding agent are deteriorated, and both cannot be kneaded well due to differences in viscosity and melting point.

  In injection molding, the molding material is usually put into a hopper of an injection molding machine, sent to a cylinder by a screw whose rotation speed is set so that the molding material is uniformly mixed, and then injected into a mold and molded. Is done.

In this case, the temperature of the cylinder is appropriately selected in the range of usually 150 to 400 ° C, preferably 200 to 350 ° C, more preferably 230 to 330 ° C. If the cylinder temperature is too low, fluidity will deteriorate, causing shrinkage and distortion in the molded product, and if the cylinder temperature is excessively high, silver streaks will occur due to thermal decomposition of the resin, or the molded product will turn yellow. Defects may occur. In addition, when the injection speed from the cylinder to the mold is 10 to 1,000 cm ³ / sec, it is excellent in appearance and can be molded into a large molded article, which is preferable.

The injection pressure from the cylinder to the mold is usually in the range of 500 to 1,500 kgf / cm ² . The injection pressure at this time may be appropriately selected and set in consideration of conditions such as mold design and fluidity of the molding material used.

The holding pressure is a pressure applied for a certain period of time until the molten resin at the gate portion of the mold is completely cooled and solidified after the mold is substantially filled with the injection pressure. The upper limit of the holding pressure is generally set within the range of the mold clamping pressure, but is usually 2,000 kgf / cm ² or less, preferably 1,700 kgf / cm ² or less, more preferably 1,500 kgf / cm. It is set within a range of ² or less. By setting the upper limit value of the holding pressure in such a range, there is no possibility of forming defects such as distortion in the molded body. The lower limit of the pressure holding at least 100 kgf / cm ² or higher, preferably 120 kgf / cm ² or more, more preferably set in the 150 kgf / cm ² or more ranges. By setting the lower limit value of the holding pressure in such a range, the occurrence of sink marks in the molded body can be prevented, the molding shrinkage rate can be reduced, and a product with excellent dimensional accuracy can be obtained.

  The mold temperature at this time is usually set at a temperature lower than the glass transition temperature (Tg, X) of the thermoplastic saturated norbornene-based resin, preferably 5-100 ° C. lower than the Tg of the resin. Preferably, it is set at a temperature in the range of 10-60 ° C. lower than Tg. By setting the mold temperature in such a range, the distortion of the molded body can be suppressed low.

  In addition, the molding resin can be preliminarily dried for the purpose of reducing the color tone of the molded body and the generation of oxides and voids as much as possible. As the drying conditions, it is preferable to perform vacuum drying at a temperature of 100 to 110 ° C. and a time of 4 to 12 hours, or to flow nitrogen from a hopper portion of an injection molding machine and replace with air.

The molded body thus obtained has a thickness t (μm) of 500 μm or less, and the area S (μm ² ) of the main surface of the molded body is

This is a thin injection molded body.
According to the present invention, when producing such a thin injection-molded body, (a) a thermoplastic saturated norbornene-based resin is selected from the viewpoints of transparency, molding processability, mechanical strength, and the like (b) Among thermoplastic saturated norbornene-based resins, it has a specific melt mass flow rate (MFR) and glass transition temperature (X), and the relationship between the weight average molecular weight (Y) and the glass transition temperature (X) is specific. By using such a material, it is possible to provide a thin molded article having excellent transferability, heat resistance and strength characteristics (no cracking at the time of release and no cracking in the stress test).

The molded product of the present invention is excellent in mechanical toughness. Its flexural strength is not particularly limited, and preferably 300 kgf / cm ² or more, more preferably 500 kgf / cm ² or more. The bending strength of the injection molded body can be measured using a known bending strength measuring device based on, for example, ASTM D790.

  The molded product of the present invention is also excellent in impact strength. The DuPont impact strength (R = 1/2 inch, 50% fracture energy) measured according to JIS-K7211 of the molded article of the present invention is preferably 0.9 J or more.

  Since the molded article of the present invention is excellent in transparency, heat resistance and low water absorption, and has mechanical toughness as described above, it is particularly useful as an optical material in a wide range of fields. For example, light guide plate, light diffusion plate, optical disk, optical fiber, optical card, optical lens, Fresnel lens, lenticular lens, optical mirror, liquid crystal display element substrate, polarizing film, retardation film, light diffusion sheet, prism sheet, light collecting sheet And window materials for automobiles, roof materials, window materials for aircraft, window materials for vending machines, show window materials, showcase materials, and the like. Light guide plates are particularly preferred.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, “part” or “%” is based on weight unless otherwise specified, and pressure is gauge pressure.
Various physical properties were measured according to the following methods.

(1) Molecular weight The number average molecular weight (Mn), the weight average molecular weight (Mw, Y) and the molecular weight distribution (MWD) were measured as standard polyisoprene equivalent values by gel permeation chromatography (GPC) using cyclohexane as a solvent.
(2) Hydrogenation rate The hydrogenation rate of the norbornene-based ring-opening polymer was calculated by measuring a ¹ H-NMR spectrum.

(3) Glass transition temperature (Tg, X)
Tg was measured by the differential operating calorimetry (DSC) method.
(4) Melt mass flow rate (MFR)
Based on JIS-K-6719, it measured on the conditions of 230 degreeC and load 2.16kg.

(5) Releasability A V-shaped ridge line (height 80 μm, angle 110 °) having a light reflection function on one surface of the cavity surface is parallel to the light incident surface and re-entered from the light incident surface side. A light guide plate (by a mold clamp pressure of 850 tons, a resin temperature of 260 ° C., a mold temperature of 110 ° C.) by injection molding using a plurality of stampers formed so that the interval gradually becomes narrower toward the optical surface side. 20 sheets of length 35 mm × width 46 mm × thickness 0.45 mm; main surface area S (μm ² ) = 35 × 10 ³ × 46 × 10 ³ = 1610 × 10 ⁶ ) were produced.
Of the 20 sheets, the number of sheets that cracked during release was evaluated. The smaller the number of cracks, the better the releasability.

(6) Transferability of molded product The state of the V-groove having a light reflecting function formed on the surface of the light guide plate created in (5) above is observed with an optical microscope, and the groove is particularly formed in a portion where the groove is most dense. ◎ (very good) that the edge part is not buried and the edge part has not lost the corner, ○ (good) that the groove part is not filled even if the edge part has some corners missing A case where some of the groove was buried was evaluated as Δ (slightly defective), and a case where the dense part of the groove was completely crushed was evaluated as x (defective).

(7) Bending strength Resin plate (length 100 mm × width 10 mm × thickness 0.5 mm; surface area S (μm ² ) by injection molding (clamping pressure 500 MPa, resin temperature 260 ° C., mold temperature 110 ° C.) ) = 100 × 10 ³ × 10 × 10 ³ = 1000 × 10 ⁶ ), and based on ASTM D790, the distance between supporting points is 30.0 mm, the temperature is 23 ° C., the humidity is 50%, and the condition is 10 hours after molding. It measured with the bending strength measuring apparatus (Autograph AGS-10kND, Shimadzu Corp. make). It evaluated as the average value measured about five test pieces (the 1st place of the average value was rounded off).

(8) Impact strength Resin plate (length 40 mm × width 40 mm × thickness 0.5 mm; surface area S (μm ² ) by injection molding (clamping pressure 500 MPa, resin temperature 260 ° C., mold temperature 110 ° C.) ) = 40 × 10 ³ × 40 × 10 ³ = 1600 × 10 ⁶ ). After treatment in an oven at 105 ° C. for 24 hours, the DuPont impact strength (R = 1/2 inch, 50% fracture energy) was measured at room temperature in accordance with JIS-K7211, and the average value measured for five test pieces Evaluation (rounded to the first decimal place of the average value).

[Example 1]
In a dry, nitrogen-substituted polymerization reactor, 30% tetracyclododecene (hereinafter abbreviated as “TCD”), 50 mol% dicyclopentadiene (hereinafter abbreviated as “DCP”), and 1,4- 10 parts of a monomer mixture consisting of 20 mol% methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter abbreviated as “MTF”), 300 parts of dehydrated cyclohexane, 1.05 of 1-hexene as a molecular weight regulator Part, diisopropyl ether 0.2 part, isobutyl alcohol 0.18 part, triisobutylaluminum 0.48 part, and tungsten hexachloride 0.77 wt% toluene solution 15 part were added and stirred at 50 ° C. for 10 minutes.
Thereafter, 90 parts of the monomer mixture and 25 parts of a 0.77% by weight tungsten hexachloride toluene solution were continuously dropped into the polymerization reactor over 2 hours while stirring, and further stirred for 30 minutes after completion of the dropping. Thereafter, 0.5 part of isopropyl alcohol was added to terminate the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion ratio of the monomer to the polymer was 100%.

  Next, 300 parts of the polymerization reaction solution containing the above polymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and 10 parts of a diatomaceous earth-supported nickel catalyst (G-96D, manufactured by Zude Chemie Catalyst, nickel support rate of 58% by weight) were added. It was. After replacing the inside of the autoclave with hydrogen, the reaction was carried out at 180 ° C. under a hydrogen pressure of 4.5 MPa for 10 hours. After completion of the hydrogenation reaction, the filter is filtered under pressure at a pressure of 0.25 MPa using a pressure filter (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) using Radiolite # 800 as a filter bed to obtain a colorless and transparent solution. It was. Subsequently, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 0.1 as an antioxidant per 100 parts of the polymer solid content was added to the obtained solution. Part by weight was added and dissolved. After filtering this solution through a metal fiber filter (pore size 0.5 μm, manufactured by Nichidai), the filtrate was filtered through “Zeta Plus Filter 30S” (pore size 0.5-1 μm, manufactured by Cuno), Foreign matter was removed by filtration with a metal fiber filter (pore size 0.2 μm, manufactured by Nichidai).

  Next, the filtrate obtained above was heated to 250 ° C. with a preheating device, and continuously supplied to a cylindrical concentration dryer (manufactured by Hitachi, Ltd.) at a pressure of 3 MPa. The operating conditions of the concentration dryer were adjusted such that the pressure was 60 kPa and the temperature of the concentrated polymer solution inside was 290 ° C. The concentrated solution was continuously derived from the concentration dryer, and further supplied to the same type of concentration dryer at a pressure of 1.5 MPa while maintaining the temperature at 290 ° C. The operating conditions were a pressure of 1.5 kPa and a temperature of 290 ° C. The polymer in the molten state is continuously derived from a concentrating dryer, extruded from a die in a class 100 clean room, water-cooled, and then cut with a pelletizer (OSP-2, manufactured by Nagata Seisakusho) to produce a ring-opened polymer hydride. 1 pellet was obtained.

This ring-opened polymer hydride 1 had Mw of 24,000, Mn of 10,400, MWD of 2.31, hydrogenation rate of 99.9%, Tg of 125 ° C., and MFR of 9 g / 10 min. .
Next, using the obtained ring-opening polymer hydride 1 pellets, the above-mentioned (5) releasability test, (6) molded product transfer test, (7) bending strength test, and ( The impact strength test of 8) was conducted. The evaluation results of each test are shown in Table 1.

[Example 2]
A ring-opened polymer hydride 2 was obtained in the same manner as in Example 1 except that the composition of the monomer mixture was TCD 15%, DCP 70%, and MTF 15%.
The addition rate of the monomer of the polymerization reaction solution to the polymer was 99.8%. Mw of the obtained ring-opening polymer hydride 2 was 26,000, Mn was 11,500, MWD was 2.26, hydrogenation rate was 99.9%, Tg was 115 ° C., and MFR was 9 g / 10 min. there were.

  Next, pellets of the obtained ring-opened polymer hydride 2 were produced in the same manner as in Example 1, and using the pellets, the releasability test of (5) and the transfer of the molded product of (6) were performed. Test, bending strength test (7), and impact strength test (8). The evaluation results of each test are shown in Table 1.

[Example 3]
A cyclohexane solution of bicyclo [2.2.1] hept-2-ene (hereinafter abbreviated as “NB”) from the upper part of a 1 m ³ polymerization vessel equipped with a stirring blade is supplied with a concentration of NB in the polymerization vessel. It supplied continuously so that it might be set to 60 kg / m < ³ >. As a catalyst from the upper part of the polymerization vessel, a cyclohexane-based solution of VO (OC ₂ H ₅ ) Cl ₂ was added so that the vanadium concentration in the polymerization vessel became 0.8 mol / m ^3, and ethylaluminum sesquichloride (Al (C A cyclohexane solution of ₂ H ₅ ) _1.5 Cl _1.5 ) was continuously fed into the polymerization vessel so that the aluminum concentration in the polymerization vessel was 7.2 mol / m ³ . Further, ethylene was supplied at a rate of 80 m ³ / hour, nitrogen at 45 m ³ / hour, and hydrogen at 6 m ³ / hour using a bubbling tube in the polymerization system.

A copolymerization reaction was carried out while maintaining a polymerization system in which a heat medium was circulated in a jacket attached to the outside of the polymerization vessel at 10 ° C. The copolymer polymerization solution produced by the above copolymerization reaction is continuously from the top of the polymerization vessel so that the polymerization solution in the polymerization vessel is always 1 m ³ (that is, the average residence time is 0.5 hour). Extracted. A cyclohexane / isopropyl alcohol (1: 1) mixed solution was added to the extracted polymerization solution to stop the polymerization reaction.
Thereafter, an aqueous solution obtained by adding 5 liters of concentrated hydrochloric acid to 1 m ^{3 of} water was brought into contact with the mixture at a ratio of 1: 1 with vigorous stirring, and the catalyst residue was transferred to the aqueous phase. After leaving this contact liquid mixture, the aqueous phase was separated and removed, and further washed with water twice to purify and separate the polymerization liquid phase.

Next, the purified and separated polymer solution was brought into contact with 3 times the amount of acetone under strong stirring to precipitate a copolymer, and then the solid part (copolymer) was collected by filtration and sufficiently washed with acetone. Furthermore, in order to extract unreacted monomers present in the polymer, this solid part was put into acetone so as to be 40 kg / m ^3, and then extracted at 60 ° C. for 2 hours. It was. After the extraction treatment, the solid part was collected by filtration and dried at 130 ° C. and 0.47 MPa for 12 hours under a nitrogen flow.

  The NB content of the ethylene / NB copolymer 3 obtained as described above was 50 mol%, the Mw was 77,000, the Tg was 132 ° C., and the MFR was 11 g / 10 min.

  Next, the obtained ethylene / NB copolymer 3 pellets were produced in the same manner as in Example 1, and using the pellets, the releasability test of (5) above and the transferability of the molded body of (6). The test, the bending strength test (7), and the impact strength test (8) were conducted. The evaluation results of each test are shown in Table 1.

[Comparative Example 1]
A ring-opened polymer hydride 4 was obtained in the same manner as in Example 1 except that the amount of 1-hexene was 1.5 parts. The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%.
The hydrogenated ring-opened polymer hydride 4 obtained by hydrogenation had Mw of 21,000, Mn of 9,000, MWD of 2.33, hydrogenation rate of 99.9%, Tg of 125 ° C., MFR Was 15 g / 10 min.
Next, pellets of the obtained ring-opened polymer hydride 4 were produced in the same manner as in Example 1, and using the pellets, the releasability test of the above (5) and the transferability of the molded body of (6). The test, the bending strength test (7), and the impact strength test (8) were conducted. The evaluation results of each test are shown in Table 1.

[Comparative Example 2]
The same operation as in Example 1 described in JP-A-5-47034 was carried out to obtain 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octa. A ring-opening polymer hydride 5 of hydronaphthalene was obtained.
The addition rate of the monomer of the polymerization reaction solution to the polymer was 99.8%. The obtained ring-opening polymer hydride 5 had Mw of 28,000, Mn of 11,000, MWD of 2.82, hydrogenation rate of 99.9%, Tg of 152 ° C., and MFR of 2 g / 10 min. there were.

  Next, pellets of the obtained ring-opened polymer hydride 5 were produced in the same manner as in Example 1, and using the pellets, the releasability test of (5) above and the transferability of the molded body of (6). The test, the bending strength test (7), and the impact strength test (8) were conducted. The evaluation results of each test are shown in Table 1.

[Comparative Example 3]
JP by an operation similar to that in Example 3 of 2000-219725 JP, 8-ethyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] Dodeca-3-ene 15%, DCP 85% of the ring-opening polymer hydride 6 consisting of monomers was obtained.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. Mw of the obtained ring-opening polymer hydride 6 was 28,500, Mn was 12,000, MWD was 2.37, hydrogenation rate was 99.9%, Tg was 103 ° C., and MFR was 8 g / 10 min. there were.

  Next, pellets of the obtained ring-opened polymer hydride 6 were produced in the same manner as in Example 1. Using these pellets, the releasability test of (5) above and the transferability of the molded body of (6). The test, the bending strength test (7), and the impact strength test (8) were conducted. The evaluation results of each test are shown in Table 1.

[Comparative Example 4]
The same operation as in Example 1 described in JP 2000-169558 A was performed to obtain an ethylene / NB addition copolymer 7 composed of 53 mol% of NB. Mw of the obtained ethylene / NB addition copolymer 7 was 36,000, Mn was 15,200, MWD was 2.36, Tg was 140 ° C., and MFR was 5 g / 10 min.

  Next, pellets of the obtained ethylene / NB copolymer 7 were produced in the same manner as in Example 1. Using these pellets, the releasability test of (5) above and the transferability of the molded body of (6). The test, the bending strength test (7), and the impact strength test (8) were conducted. The evaluation results of each test are shown in Table 1.

From Table 1, the thermoplastic saturated norbornene of Examples 1 to 3 having a glass transition temperature (X) of 115 to 132 ° C., an MFR of 9 g / 10 min to 11 g / 10 min, and a weight average molecular weight (Y) greater than Y ^0. The injection-molded product obtained from the system resin was excellent in all of mold release property, transfer property, bending strength, and impact strength.

On the other hand, Y is in the injection molded article obtained from the Y ⁰ of less than Comparative Example 1 Thermoplastic saturated norbornene resin, releasability, flexural strength and impact strength was insufficient.
Y is an injection molded article obtained from the Y ⁰ smaller Comparative Example 2 Thermoplastic saturated norbornene resin, releasability, although excellent in bending strength and impact strength were inferior transferability.
The injection molded product obtained from the thermoplastic saturated norbornene resin of Comparative Example 3 having a glass transition temperature (X) as low as 103 ° C. was inferior in impact strength (unmeasurable).
Y is an injection molded article obtained from the thermoplastic saturated norbornene resin Y ⁰ less than Comparative Example 4, the releasing resistance, flexural strength and impact strength was inferior. Also, the transferability was insufficient from a practical viewpoint.

Claims (4)

The thickness t (μm) is 500 μm or less, and the area S (μm ² ) of the main surface of the molded body is

A molded body which is
(1) The melt mass flow rate (MFR) at 230 ° C. and a load of 2.16 kg is in the range of 5 to 16 g / 10 minutes,
(2) The glass transition temperature (X) is 110 ° C. or higher, and
(3) The weight average molecular weight (Y) is

A molded product formed by injection molding a thermoplastic saturated norbornene resin in the range of   The molded article according to claim 1, wherein the thermoplastic saturated norbornene resin is a hydride of a norbornene ring-opening polymer. The molded body according to claim 1 or 2, wherein the bending strength is 300 kgf / cm ² or more. It is a light-guide plate, The molded object in any one of Claims 1-3.