JP5682321B2 - Norbornene-based ring-opening copolymer hydride and use thereof - Google Patents

Description

  The present invention relates to a polymer having a good balance of fluidity, heat resistance, transparency and strength.

Since the norbornene-based ring-opening polymer hydride is excellent in properties such as transparency, low birefringence, heat resistance, and low water absorption, it is mainly used for optical lenses such as camera lenses and pickup lenses, optical films, light guide plates, It is used in the optical field such as a light diffusion plate.
With the recent rapid technological progress, there is an increasing demand for thin molded bodies in the optical field. For example, in camera-equipped mobile phones, with the miniaturization of the phone body and the increase in the number of mounted lenses, there is a strong demand for thinner and more precise lenses, and there is a demand for resins with excellent fluidity. ing. However, the fluidity of the conventional norbornene-based ring-opening copolymer hydride may be insufficient.

  As a method for improving the fluidity of the hydride of norbornene-based ring-opening copolymer, there is a method of lowering the glass transition temperature or molecular weight of hydride of norbornene-based ring-opening copolymer. There was a problem that decreased.

Patent Document 1 describes that a wax is added to a hydride of a norbornene-based ring-opening polymer to provide a molding material having excellent fluidity and having a high strength and excellent surface accuracy. ing.
However, when such a molding material is used, there is a problem that the mold is easily soiled at the time of molding, which causes defects in the molded product, and the productivity is lowered due to the cleaning of the mold.

  Patent Document 2 is a polymer in which straight chains having 2 or more carbon atoms and hydrocarbon rings are alternately arranged, and the proportion of straight chains having 3 or more carbon atoms is 5 to 95% by weight in the entire straight chain. % Cyclic olefin-based ring-opening polymer and hydride thereof have a high elastic recovery property, an appropriate elastic modulus, and excellent transparency and heat resistance. Specifically, a structural unit derived from dicyclopentadiene / a structure derived from cyclopentene obtained by using cyclopentene as a monomer giving a straight chain having 3 or more carbon atoms and copolymerizing it with dicyclopentadiene and hydrogenating it. Cyclic olefin ring-opening polymer hydrides having units of 56/44 to 45/55 are disclosed.

JP 2009-138111 A JP 2002-220440 A

  The present inventors examined improvement in fluidity of a norbornene-based ring-opening copolymer hydride. As a result, a norbornene-based ring-opening copolymer hydride composed of a copolymer of cyclopentene and a norbornene-based monomer was obtained. It was found that the fluidity was excellent. However, in monocyclic monoolefins such as cyclopentene, the conversion rate of monocyclic olefins to polymers during the polymerization reaction is low, and the variation in the conversion rate is large. Therefore, norbornene-based ring-opening copolymer hydride It has been found that there is a problem in that there are large variations in quality such as glass transition temperature and fluidity.

  In addition, the present inventors have continued earnestly studying the copolymer of a monocyclic olefin and a norbornene monomer, and using a monocyclic non-conjugated polyene instead of the monocyclic monoolefin, and When the proportion of structural units derived from monocyclic non-conjugated polyenes in the polymer is within a relatively small predetermined range, the conversion rate to the polymer during the polymerization reaction is high and the variation in the conversion rate is small. It has been found that the stability of quality such as transition temperature and fluidity is high, and that the resulting norbornene-based ring-opening copolymer hydride is excellent in fluidity and strength.

Thus, according to the present invention, a norbornene-based ring-opening copolymer obtained by hydrogenating a norbornene-based ring-opening copolymer obtained by ring-opening polymerization of a monocyclic non-conjugated polyene and a norbornene-based monomer. A norbornene-based ring-opening characterized in that a molar content ratio of a hydride-containing structural unit derived from a monocyclic non-conjugated polyene and a structural unit derived from a norbornene-based monomer is 1/99 to 20/80 Copolymer hydrides are provided.
The norbornene monomer preferably contains 50 mol% or more of a tricyclic or higher norbornene monomer.
Moreover, according to this invention, the molded object which consists of said norbornene-type ring-opening copolymer hydride is provided.
The molded body is preferably an optical lens, and an optical lens manufactured by injection molding is particularly preferable.

  ADVANTAGE OF THE INVENTION According to this invention, the norbornene-type ring-opening copolymer hydride excellent in the balance of fluidity | liquidity, heat resistance, transparency, and intensity | strength is provided.

  The hydrogenated norbornene-based ring-opening copolymer of the present invention is obtained by hydrogenating a norbornene-based ring-opening copolymer obtained by ring-opening polymerization of a monocyclic non-conjugated polyene and a norbornene-based monomer. .

1) Norbornene-based ring-opening copolymer The norbornene-based ring-opening copolymer used in the present invention is obtained by ring-opening polymerization of a norbornene-based monomer and a monocyclic non-conjugated polyene.

Norbornene-based monomers As norbornene-based monomers, bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo [2.2.1] hept-2- Bicyclic monomers such as ene (common name: ethylidene norbornene) and derivatives thereof (having substituents in the ring); tricyclo [4.3.0 ^1,6 . Tricyclic monomers such as 1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof; 7,8-benzotricyclo [4.3.0.1 ^{2, 5} ] Dec-3-ene (common name: methanotetrahydrofluorene: also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and its derivatives, and the like, and the like.
Examples of the substituent include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group, and the norbornene-based monomer may have two or more of these. Specifically, 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-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers are used alone or in combination of two or more. Among these, from the viewpoint of heat resistance, the amount of the bicyclic monomer contained in the total norbornene monomer is preferably 0 to 50 mol%, more preferably 0 to 15 mol%. The total amount of the tricyclic or higher monomer contained in the system monomer is preferably 50 mol% or more, more preferably 70 mol% or more. Particularly in the field where heat resistance is required, the amount of the tetracyclic monomer is preferably 40 to 100 mol%.

-Monocyclic non-conjugated polyene The monocyclic non-conjugated polyene used in the present invention includes 1,4-cyclohexadiene and its derivatives (having a substituent in the ring), 1,5-cyclooctadiene and its derivatives ( Having a substituent in the ring), 1,5-cyclodecadiene, 1,5,9-cyclododecatriene and its derivatives (having a substituent in the ring), 1,5,9,13-cyclohexadeca Tetraene and derivatives thereof (having a substituent in the ring) and the like.
Examples of the substituent include an alkyl group, an alkylene group, an aryl group, a silyl group, an alkoxycarbonyl group, and an alkylidene group. The monocyclic nonconjugated polyene monomer may have two or more of these. Good. Specific examples include 3-methyl-cycloocta-1,5-diene and 9-phenyl-1,5-cyclododecadiene.

  When a monocyclic monoene is used instead of a monocyclic non-conjugated polyene, the conversion rate of the monocyclic monoene to the polymer is low, and the variation in the conversion rate is large. The stability of hydride quality such as glass transition temperature and fluidity is low. In addition, when a monocyclic conjugated polyene is used instead of the monocyclic non-conjugated polyene, the polymerization conversion rate of the norbornene monomer and the monocyclic conjugated polyene is remarkably lowered.

  Examples of the copolymer obtained by copolymerizing the above monomer with a monocyclic non-conjugated polyene include random copolymers, block copolymers such as diblocks, triblocks, and higher multiblocks. However, a random copolymer is preferable from the viewpoint of heat resistance.

-Ring-opening polymerization method The ring-opening polymerization of the norbornene-based monomer can be performed according to a known method using a metathesis polymerization catalyst. The metathesis polymerization catalyst is not particularly limited and known ones are used. Specifically, for example, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a metal halide or acetylacetone compound selected from the group consisting of a co-catalyst and an organoaluminum compound; or JP-A-7-179575; Am. Chem. Soc. 1986, 108, p. 733, J. et al. Am. Chem. Soc. 1993, 115, p. 9858, and J.H. Am. Chem. Soc. 1996, 118, p. A known Schrock-type or Grubbs-type living ring-opening metathesis catalyst disclosed in No. 100 and the like can be used.

  These catalysts are used alone or in combination of two or more. The amount of the catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 1 / 1,000,000 to 1/10, preferably 1 / 100,000 to 1 in terms of molar ratio to the total amount of monomers. 1/100.

  In the ring-opening polymerization of the norbornene monomer and the monocyclic non-conjugated polyene, a linear α-olefin can be used as a molecular weight regulator. Examples of the linear α-olefin include those having 4 to 40 carbon atoms such as 1-butene, 1-hexene and 1-decene.

  The addition amount of the linear α-olefin is usually 0.1 to 3 mol, preferably 0.3 to 2 mol, more preferably 0.5 to 1.5 mol with respect to 100 mol of all monomers. .

Furthermore, polar compounds can be added to increase polymerization activity and ring-opening polymerization selectivity. Examples of polar compounds include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, and others And Lewis acid.
As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like. These polar compounds are used alone or in combination of two or more. The dose is appropriately selected, but the ratio with the metal in the catalyst, that is, the polar compound / metal ratio (molar ratio), is usually in the range of 1 to 100,000, preferably 5 to 10,000. is there.

  The polymerization reaction may be performed in a solvent such as an organic solvent. The solvent is not particularly limited as long as it is inert to the polymerization reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin and bicyclononane; halogenated hydrocarbons such as dichloroethane, chlorobenzene, dichlorobenzene and trichlorobenzene;

  The form of polymerizing the norbornene-based ring-opening copolymer used in the present invention is not particularly limited, but a batch polymerization method (batch method), a monomer continuous addition method (a method of proceeding polymerization by continuously adding monomers), etc. In particular, it is preferable to use a continuous monomer addition method because it has a more random chain structure.

  As a method for adding the linear α-olefin, after adding the whole amount of the linear α-olefin to the solvent, a method of continuously adding the norbornene monomer, the linear α-olefin is added simultaneously with the norbornene monomer. The method of adding continuously etc. is mentioned, The method of adding a linear alpha olefin continuously simultaneously with a norbornene-type monomer has a random chain structure especially.

The polymerization temperature is usually in the range of −50 ° C. to 250 ° C., preferably −30 ° C. to 200 ° C., more preferably −20 ° C. to 150 ° C. The polymerization pressure is usually in the range of 0 to 50 kg / cm ² , preferably 0 to 20 kg / cm ² . The polymerization time is appropriately selected depending on the polymerization conditions, but is usually in the range of 30 minutes to 20 hours, preferably 1 to 10 hours.

  The number average molecular weight (Mn) of the norbornene-based ring-opening copolymer used in the present invention is usually 5,000 to 100,000, preferably 6,000 to 70,000, more preferably 7,000 to 60,000. The weight average molecular weight (Mw) is usually 10,000 to 350,000, preferably 12,000 to 245,000, more preferably 14,000 to 210,000. The molecular weight is measured by gel permeation chromatography (GPC) using cyclohexane as a solvent, and is expressed as a standard polyisoprene conversion value. When the molecular weight is within these ranges, the balance between mechanical strength and moldability is excellent. The molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably in the range of 1 to 5, more preferably 1 to 4.

2) Hydride of norbornene-based ring-opening copolymer The hydrogenated norbornene-based ring-opening copolymer of the present invention is obtained by hydrogenating a carbon-carbon double bond in the norbornene-based ring-opening copolymer. It is done.

  In the hydride of norbornene-based ring-opening copolymer of the present invention, the molar content ratio of the structural unit derived from monocyclic non-conjugated polyene and the structural unit derived from norbornene-based monomer is 1/99 to 20/80, preferably Is 3/97 to 17/83. When there are many structural units derived from monocyclic non-conjugated polyene, the heat resistance of the norbornene-based ring-opening copolymer hydride is lowered. When the number of structural units derived from monocyclic non-conjugated polyene is small, fluidity and strength are lowered.

  The molar content ratio between the structural unit derived from monocyclic nonconjugated polyene and the structural unit derived from norbornene monomer is the mixing ratio of monocyclic nonconjugated polyene and norbornene monomer during ring-opening polymerization, polymerization conversion What is necessary is just to adjust suitably according to a rate.

-Hydrogenation catalyst and hydrogenation method Hydrogenation can be carried out by bringing a norbornene-based ring-opening copolymer into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. Examples of the hydrogenation catalyst include JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, JP-A-7-41550, and the like. What is described can be used.
The catalyst may be homogeneous or heterogeneous. Homogeneous catalyst is easy to disperse in the hydrogenation reaction solution, so it can be added in a small amount, and since it is active without high temperature and pressure, the polymer does not decompose or gel, and low cost and stable quality It is superior to sex. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are easy to remove.

  Examples of the homogeneous catalyst include, for example, a Wilkinson complex, that is, a catalyst comprising a combination of chlorotris (triphenylphosphine) rhodium (I); a transition metal compound and an alkyl metal compound, specifically, cobalt acetate / triethylaluminum, nickel acetyl Examples include combinations of acetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethylmagnesium, and the like.

  Examples of the heterogeneous catalyst include a catalyst in which a hydrogenation catalyst metal such as Ni, Pd, Pt, Ru, and Rh is supported on a carrier. In particular, in the case where it is preferable that the amount of impurities or the like is less, it is preferable to use an adsorbent such as alumina or diatomaceous earth as a carrier.

The hydrogenation reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the catalyst, but a hydrocarbon solvent is usually used because of the excellent solubility of the hydride produced. Examples of the hydrocarbon solvent include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin, and bicyclononane; Among these, low boiling point alicyclic hydrocarbons such as cyclohexanone are preferable.
These organic solvents can be used alone or in combination of two or more. Usually, it may be the same as the polymerization reaction solvent, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted.

When the norbornene-based ring-opening copolymer hydride according to the present invention has a repeating unit having an aromatic ring, in the hydrogenation reaction of a carbon-carbon double bond in the main chain structure, a side chain aromatic ring The group structure can remain, but may be completely hydrogenated. In addition, the carbon-carbon double bond in the main chain structure can be distinguished from the unsaturated bond in the aromatic ring structure by analysis by ¹ H-NMR.

The hydrogenation reaction may be performed according to a conventional method.
The hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature, and when the norbornene monomer has an aromatic ring, the residual rate of the aromatic ring can also be changed. When the above hydrogenation catalyst is used, in order to leave the unsaturated bonds of the aromatic ring to a certain extent or more, control such as lowering the reaction temperature, lowering the hydrogen pressure, or shortening the reaction time can be performed. Good.

After completion of the hydrogenation reaction, the catalyst can be removed according to a conventional method such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added. In applications where it is not preferable that the transition metal remains, such as medical equipment, the transition metal is substantially prevented from remaining. In order to obtain such a norbornene-based ring-opening polymer hydride, an adsorbent such as alumina having a specific pore volume and specific surface area as disclosed in JP-A-5-317411 It is preferable to wash the norbornene-based polymer hydride solution with acidic water and pure water.
The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used, and it is preferable to use a filter aid such as diatomaceous earth or pearlite from the viewpoint of efficiency.

  The number average molecular weight of the hydride of norbornene-based ring-opening copolymer used in the present invention is usually 5,000 to 100,000, preferably 6,000 to 70,000, more preferably 7,000 to 60,000. is there. The weight average molecular weight is usually 10,000 to 350,000, preferably 12,000 to 245,000, more preferably 14,000 to 210,000. The molecular weight is measured by gel permeation chromatography (GPC) using cyclohexane as a solvent, and is expressed as a standard polyisoprene conversion value. When the molecular weight is within these ranges, the solution stability, the balance between mechanical strength and moldability are excellent. The molecular weight distribution (Mw / Mn) is not particularly limited, but is preferably in the range of 1 to 5, more preferably 1 to 4.

The glass transition temperature (Tg) of the hydride of norbornene-based ring-opening copolymer used in the present invention is usually 100 to 200 ° C, preferably 110 to 170 ° C. If the Tg is low, the heat resistance is low and the use environment may be limited. If the Tg is high, the fluidity is lowered and the moldability may be deteriorated.
The glass transition temperature of the norbornene-based ring-opening copolymer hydride can be measured based on JIS K 7121 using a differential scanning calorimeter.

In the hydride of norbornene-based ring-opening copolymer used in the present invention, the hydrogenation rate of the main chain double bond of the hydride of norbornene-based ring-opening copolymer is usually 80% or more, preferably 90% or more, more preferably 95 % Or more, more preferably 99% or more, particularly preferably 99.9% or more. A high hydrogenation rate is preferable in that it is excellent in heat resistance and moisture resistance, and resin burning hardly occurs during molding, and particularly when a film is formed, generation of die lines can be suppressed.
The hydrogenation rate of the norbornene-based ring-opening copolymer hydride can be determined by measuring by ¹ H-NMR using deuterated chloroform as a solvent.

3) Molded body The molded body of the present invention is molded from a hydride of the norbornene-based ring-opening copolymer, which is blended with other polymer materials suitable for application fields, various additives, etc., if necessary. Can be obtained.

(1) Other polymer materials Examples of other polymer materials include (a) rubbery polymers and (b) other thermoplastic resins.

B) Rubber polymer As the rubber polymer, for example, ethylene-α-olefin copolymer rubber; ethylene-α-olefin-polyene copolymer rubber; ethylene such as ethylene-methyl methacrylate and ethylene-butyl acrylate; Copolymer with unsaturated carboxylic acid ester; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. Polymer of alkyl acrylate ester; polybutadiene, polyisoprene, styrene-butadiene or styrene-isoprene random copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylate alkyl ester Diene rubber such as copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile copolymer, butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprestyrene-butadiene block copolymer Polymers, aromatic vinyl-conjugated diene block copolymers such as hydrogenated styrene-butadiene block copolymers, styrene-isoprene block copolymers, hydrogenated styrene-isoprene block copolymers, low crystalline polybutadiene resins, ethylene -A propylene elastomer, a styrene graft ethylene-propylene elastomer, a thermoplastic polyester elastomer, an ethylene-type ionomer resin etc. can be mentioned.
Of these thermoplastic elastomers, a hydrogenated styrene-butadiene block copolymer, a hydrogenated styrene-isoprene block copolymer, and the like are preferable. Specifically, JP-A-2-133406 and JP-A-2- Examples thereof include those described in JP-A-305814, JP-A-3-72512, JP-A-3-74409, and the like.

When the molding material is used as a medical container material, it is required not to lower the transparency of the medical container during heat and pressure treatment such as steam sterilization (steam sterilization). By doing so, whitening during steam sterilization can be effectively prevented.
In this case, the blending ratio of the rubbery polymer is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, more preferably 100 parts by weight of the hydride of norbornene-based ring-opening copolymer. It is the range of 0.01-3 weight part.

  When high impact resistance and flexibility are required, the blending ratio of the rubbery polymer is usually 0.1 to 100 parts by weight, preferably 1 with respect to 100 parts by weight of the norbornene ring-opening copolymer hydride. It is -70 weight part, More preferably, it is the range of 5-50 weight part.

(B) Other thermoplastic resins Other thermoplastic resins include, for example, low density polyethylene, high density polyethylene, linear low density polyethylene, ultra low density polyethylene, polypropylene, ethylene-ethyl acrylate copolymer, ethylene- Different types of thermoplastic resins such as vinyl acetate copolymer, polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate, cellulose triacetate, polyetherimide, polyarylate, polysulfone, polyethersulfone, and the above-mentioned norbornene Examples include hydrides of norbornene-based ring-opening copolymers other than hydrides of ring copolymers.

  These other thermoplastic resins can be used alone or in combination of two or more. The blending ratio of the other thermoplastic resin is usually 0.1 to 100 parts by weight, preferably 0.5 to 70 parts by weight, more preferably 1 to 100 parts by weight based on 100 parts by weight of the borned norbornene-based copolymer. The range is 50 parts by weight.

(2) Various Additives Additives that are blended as necessary can be used without particular limitation as long as they are generally used in the application field to which they are applied. Examples of such additives include stabilizers, lubricants, ultraviolet absorbers, crystal nucleating agents, hydrochloric acid absorbers, antistatic agents, dyes, pigments, organic or inorganic fillers, slip agents, antifogging agents, natural Examples thereof include oils, synthetic oils, waxes, flame retardants, flame retardant aids, compatibilizers, crosslinking agents, crosslinking aids, plasticizers, and the like.

(A) Stabilizer Examples of the stabilizer include fatty acid metal salts such as zinc stearate, calcium stearate, and 1,2-hydroxycalcium stearate; phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Among these, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants are particularly preferable.

  These stabilizers can be used alone or in combination of two or more. The blending ratio of the stabilizer is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the borned norbornene-based copolymer.

(B) Lubricants As the lubricants, organic compounds such as esters of aliphatic alcohols, esters of polyhydric alcohols or partial esters, inorganic fine particles, and the like can be used.
Examples of the organic compound include glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate and the like.
Inorganic fine particles include Group IA, Group IIA, Group IVA, Group VI, Group VIIA, Group VIII, Group IB, Group IIB, Group IIIB, Group IVB oxides, hydroxides, sulfides, nitrides, halogens , Carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and their hydrous compounds, complex compounds centered on them, natural minerals Showing particles. The average particle size of the inorganic fine particles is not particularly limited, but is preferably 0.01 to 3 μm.

  These lubricants can be used alone or in combination of two or more. The blending ratio of the lubricant is appropriately selected according to the purpose of use. For example, the blending ratio when the molding material of the present invention is used as a film is 100 parts by weight of the norbornene-based ring-opening copolymer hydride. Usually 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight.

(C) Organic or inorganic fillers Organic or inorganic fillers include silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium oxide, calcium carbonate, sulfuric acid Calcium, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide Examples thereof include fibers, polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers. These fillers can be added alone or in combination of two or more.
The blending ratio of the filler is usually 0.1 to 50 parts by weight, preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the norbornene-based ring-opening copolymer hydride.

The method for adding these other polymer materials and various compounding agents is not particularly limited as long as these compounding components are sufficiently dispersed in the hydride of norbornene-based ring-opening copolymer. It is performed by a method of adding in any process of or in any process of the molding process.
When a rubber polymer is used as a compounding agent, for example, a method of kneading a norbornene-based ring-opening copolymer hydride in a molten state with a twin-screw kneader or the like, and after dissolving and dispersing and mixing in a suitable solvent, The solvent is removed by a solidification method, a casting method, or a direct drying method.

  The molding method of the molded body of the present invention is not particularly limited, but the microstructure of the mold may be directly transferred by a general thermoplastic resin molding method, for example, an injection molding method, a blow molding method, or the like. However, a fine structure may be transferred to the surface of a sheet or film produced by an inflation molding method, extrusion molding method, calendar molding method, solution casting method, etc. by a thermal imprinting method, etc. In this case, it is preferable to mold by an injection molding method from the viewpoint of productivity.

The method of molding an optical lens by injection molding is generally a method in which a molding material is put into a hopper of an injection molding machine, and the number of rotations is set so that the molding material is uniformly mixed, and then sent to a cylinder. It is a method of injecting into a mold. 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. If the cylinder temperature is excessively high, silver streaks will occur due to thermal decomposition of the molding material, and the molded product will turn yellow. There is a risk of forming defects.
When the injection speed from the cylinder to the mold is usually 1 to 1000 cm ³ / sec, it is suitable because it has an excellent appearance and can be molded into a large molded body.
The injection pressure from the cylinder to the mold is usually in the range of 500 to 15000 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 molding material in 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 clamping pressure of the mold, but is usually set within a range of 2000 kgf / cm ² or less, preferably 1700 kgf / cm ² or less, more preferably 1500 kgf / cm ² or less. The By setting the upper limit value of the holding pressure in such a range, there is no possibility that molding defects such as distortion occur 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) of the norbornene-based ring-opening copolymer hydride in the molding material, and preferably 10 to 100 ° C. lower than the Tg of the resin. It is a range, More preferably, it sets in the temperature of the range of 20-60 degreeC lower than Tg. By setting the mold temperature in such a range, the distortion of the molded body can be suppressed low.

  In addition, for the purpose of reducing the color tone deterioration of the molded body and the generation of oxides and voids as much as possible, preliminary drying of the molding material is performed, or nitrogen or the like is flowed from the hopper portion of the injection molding machine to replace with air. preferable. The method of preliminary drying is not limited, and for example, it is performed by vacuum drying at 100 to 110 ° C. for 4 to 12 hours.

Since the hydride of norbornene-based ring-opening polymer of the present invention is excellent in fluidity, transparency and heat resistance, it is suitable for those having a thin structure or (and) a fine pattern on the surface. Specifically, optical field such as light guide plate, diffuser plate, diffraction grating, Fresnel lens, optical disk, prism sheet; microtechnology field such as biochip, micro analysis chip, microreactor; stamper for optical or magnetic recording disk, Circuit boards such as general circuit boards (rigid printed boards, flexible printed boards, multilayer printed wiring boards, etc.), high frequency circuit boards (circuit boards for satellite communication devices, etc.); transparent conductive films (liquid crystal boards, optical memories, surface heating elements) Etc.) substrate; semiconductor encapsulant (transistor encapsulant, IC encapsulant, LSI encapsulant, LED encapsulant, etc.), electrical / electronic component encapsulant (motor encapsulant, capacitor encapsulant) Electrical and electronic fields such as sealing materials such as materials, switch sealing materials, sensor sealing materials, etc., and optics such as prism sheets and light guide plates It is suitable for a fee.
In addition, even in thick molded products, the polymer chain orientation and residual stress generated by injection molding are reduced, which may reduce stress cracking of the molded products and decrease the birefringence and refractive index changes of optical elements. Food packaging field such as bottles, returnable bottles, baby bottles, films, shrink films, liquid, powder, or solid chemical containers (liquid chemical containers for injection, ampoules, vials, prefilled syringes, infusion bags, sealed medicine bags , Press-through packages, solid drug containers, eye drop containers, etc.), sampling containers (sampling test tubes for blood tests, caps for drug containers, blood collection tubes, sample containers, etc.), medical instruments (syringes, etc.), medical instruments, etc. Sterilization containers (for scalpels, forceps, gauze, contact lenses, etc.), experimental and analytical instruments (beakers, petri dishes, flasks, samples Tubes, centrifuge tubes, etc.), medical optical parts (plastic lenses for medical examinations, etc.), piping materials (medical infusion tubes, pipes, joints, valves, etc.), artificial organs and their parts (tooth base, artificial heart, artificial) Medical fields such as tooth roots), processing or transfer containers (tanks, trays, carriers, cases, etc.), protective materials (carrier tapes, separation films, etc.), piping (pipes, tubes, valves, flow meters, filters) , Pumps, etc.), electronic parts processing equipment for liquid containers (sampling containers, bottles, ampoule bags, etc.); covering materials (for electric wires, cables, etc.), consumer and industrial electronic equipment (copiers, Computers, printers, televisions, video decks, video cameras, etc.), structural members (parabolic antenna structural members, flat antenna structural members, radar dome structural parts) Etc.) Electrical and electronic fields such as electrical insulation materials, etc., interior materials for automobiles such as room mirrors and meter covers, etc .; also used in various applications such as automotive fields such as door mirrors, fender mirrors, beam lenses, and light covers can do.

(4) Optical lens The hydride of norbornene-based ring-opening copolymer of the present invention is particularly suitable for an optical lens having a thin structure formed by injection molding because it is excellent in fluidity, transparency and heat resistance.
As a shape of the optical lens having a thin structure, the lens diameter is preferably 1 to 10 mm, more preferably 2 to 5 mm, and the lens thickness is 1/50 to 1/5, more preferably 1/25 to 1 of the lens diameter. / 10.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited only to these examples. In the following examples and comparative examples, parts and% are based on weight unless otherwise specified, and pressure is gauge pressure.

The measurement methods for various physical properties are shown below.
(1) Molecular weight The number average molecular weight (Mn), the weight average molecular weight (Mw) and the molecular weight distribution (MWD) were measured as standard polyisoprene conversion values by gel permeation chromatography (GPC) using cyclohexane as a solvent.
For measurement, HLC8120GPC manufactured by Tosoh Corporation was used.
As the standard polyisoprene, ten standard polyisoprenes manufactured by Tosoh Corporation, Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000 and 280000 were used.
The measurement was carried out under the conditions of using TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation connected in series as a column, a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.
(2) Hydrogenation rate The hydrogenation rate of the main chain and cyclic hydrocarbon structure in the hydride of norbornene-based ring-opening copolymer was calculated by measuring the ¹ H-NMR spectrum.
(3) Glass transition temperature (Tg)
Tg was measured based on JIS K 7121 using a differential scanning calorimeter at a heating rate of 10 ° C./min.
(4) Melt flow rate (MI)
MI was measured based on JIS K 7210 at 280 ° C. and a load of 2.16 kgf.
(5) Bending strength The bending strength of the norbornene-based ring-opening copolymer hydride was measured by using an injection molding machine (product name “Roboshot (registered trademark) α-100B”, manufactured by FANUC) at a resin temperature of 280 ° C. and a mold. The temperature is a glass transition temperature of norbornene-based ring-opening copolymer hydride-60 ° C. (however, Examples 1 and 4 and Comparative Examples 1 and 3 are 120 ° C.), injection speed 20 mm / sec, holding pressure 800 kgf / cm ^2. A resin plate (length 10 cm × width 1 cm × thickness 1 mm) having a length of 10 cm, a width of 1 cm, and a thickness of 1 mm is prepared. Based on ASTM D790, the distance between supporting points is 30.0 mm, the pressure is 30 MPa, the method A, Bending strength was measured using a tensile tester (product name “Autograph (registered trademark) AGS-10kND”, manufactured by Shimadzu Corporation) under conditions of a temperature of 23 ° C., a humidity of 50%, and 40 hours after molding. The larger the bending strength, the better. If it is small, the molded body will crack during molding.
(6) Haze measurement The haze of the norbornene-based ring-opening copolymer hydride was measured with an injection molding machine (product name “Roboshot (registered trademark) α-100B”, manufactured by FANUC) at a resin temperature of 280 ° C., gold Mold temperature: glass transition temperature of norbornene-based ring-opening copolymer hydride-60 ° C. (however, Examples 1 and 4 and Comparative Examples 1 and 3 are 120 ° C.), injection speed 20 mm / sec, holding pressure 800 kgf / cm ² , a resin plate having a length of 65 mm × width of 65 mm × thickness of 1 mm was prepared and measured using a haze meter (product name “NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7136. It shows that transparency is so favorable that haze (%) is small.
(7) Molded Product Appearance Evaluation of molded product appearance was performed using a mold having a cavity with a lens diameter of 4 mm and a lens thickness of 0.4 mm, a cylinder temperature of 300 ° C., and a mold temperature of a norbornene-based ring-opening copolymer. The glass transition temperature of hydride is -60 ° C. (however, Examples 1 and 4 and Comparative Examples 1 and 3 are 130 ° C.), injection speed is 15 mm / second, and pressure is 800 kgf / cm ^2. A molded product was obtained.
The obtained 100 test pieces were observed for the presence or absence of poor filling of the molded product, and evaluated according to the following criteria. In addition, about the thing with the appearance defect, the number was also described according to the table | surface (the number in () in a table | surface).
(Double-circle): The number of defective filling is 0 out of 100.
○: 1 to 4 of 100 defective fillings.
(Triangle | delta): The filling defect goods are 5-9 pieces in 100 pieces.
X: The number of defective fillings is 10 or more out of 100.
(8) Quality stability evaluation The polymerization reaction to the drying operation were carried out 5 times in total, the average conversion rate of the norbornene monomer and monocyclic olefin at the end of the polymerization reaction, and the norbornene ring-opening copolymer hydride The average value and the maximum deviation (%) were determined for the weight average molecular weight (Mw), glass transition temperature (Tg), and melt flow rate (MI).
The maximum deviation (%) was obtained by the following formula.
Maximum deviation (%) = [(maximum value (minimum value)) − average value] × 100 / average value

[Example 1]
Polymerization reaction In a dry and nitrogen-substituted polymerization reactor, 1,5-cyclooctadiene (hereinafter abbreviated as “1,5-COD”) as a monocyclic non-conjugated polyene, 6 mol%, a norbornene-based monomer tetracyclo as dimers ^(9.2.1.0 2,10 ^{.0 3, 8)} tetradeca -3,5,7,12- tetraene (hereinafter, abbreviated as "MTF".) monomer consisting of 94 mol% 7 parts of a body mixture (1% with respect to the total amount of monomers used for polymerization), 1500 parts of dehydrated toluene, 3.8 parts of 1-hexene as a molecular weight regulator, 1.3 parts of diisopropyl ether, 0.33 of isobutyl alcohol Part, 0.84 part of triisobutylaluminum and 35 parts of a tungsten hexachloride 0.66% cyclohexane solution were added and stirred at 50 ° C. for 10 minutes. Next, 693 parts of the monomer mixture and 52 parts of a 0.66% tungsten hexachloride cyclohexane solution are continuously added dropwise to the polymerization reactor over 150 minutes while maintaining the reaction system at 50 ° C. and stirring. Furthermore, after stirring for 30 minutes after completion of the dropping, 1.0 part of isopropyl alcohol was added to stop the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion rate of the monomer was 100% for both 1,5-COD and MTF.

-Hydrogenation reaction Next, 300 parts of the polymerization reaction solution containing the above ring-opening copolymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane and a diatomaceous earth-supported nickel catalyst (product name "T8400RL", manufactured by JGC Chemical Co., Ltd., nickel support) 8.0 parts) was added. After replacing the inside of the autoclave with hydrogen, the reaction was carried out for 8 hours at 170 ° C. under a hydrogen pressure of 4.5 MPa.

-Filtration operation After the hydrogenation reaction, pressure filter (product name "Hunda filter", manufactured by IHI Corporation) using diatomaceous earth (product name "Radiolite (registered trademark) # 500", Showa Chemical Industry Co., Ltd.) as a filter bed. And pressure filtration at a pressure of 0.25 MPa to obtain a colorless and transparent solution of a ring-opening copolymer hydride.
Next, 0.5 parts of pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant per 100 parts of the hydride was added to the obtained solution. Was added and dissolved.
The solution was filtered through a metal fiber filter (manufactured by Nichidai Co., Ltd., pore size: 0.4 μm) to remove foreign matters.

・ Drying operation Next, the filtrate obtained above was removed from the solution at a temperature of 260 ° C. and a pressure of 1 kPa or less using the cylindrical concentration dryer (manufactured by Hitachi, Ltd.). Extruded into a strand form in a molten state from a die directly connected to a concentrator, cooled with water, and cut with a pelletizer (product name “OSP-2”, manufactured by Nagata Seisakusho Co., Ltd.) to pellets of norbornene-based ring-opening copolymer hydride Got.

  The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, and molded product appearance inspection of this norbornene-based ring-opening copolymer hydride were carried out, and the results are shown in Table 1. It was.

  Furthermore, the said polymerization reaction-drying operation was implemented 4 times, and the quality stability of the obtained norbornene ring-opening copolymer was evaluated. The results are shown in Table 1.

[Example 2]
A norbornene-based ring-opening copolymer hydride was obtained in the same manner as in Example 1 except that 1,5-COD was changed to 16 mol% and MTF was changed to 84 mol%. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.

[Example 3]
Example 1 except that 10-mol% of 1,5-COD, 60 mol% of MTF as a norbornene-based monomer, and 30 mol% of tetracyclododecene (hereinafter abbreviated as “TCD”) were used. Thus, a hydride of norbornene-based ring-opening copolymer was obtained. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.
The results are shown in Table 1.

[Example 4]
Example 1 except that 1,5,9-cyclododecatriene (hereinafter abbreviated as “1,5,9-CDT”) as a monocyclic non-conjugated polyene was 4 mol% and MTF was 96 mol%. Similarly, a hydride of norbornene-based ring-opening copolymer was obtained. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.

[Comparative Example 1]
A norbornene-based ring-opening copolymer hydride was obtained in the same manner as in Example 1 except that the monocyclic non-conjugated polyene was not used and the MTF was 100%. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.

[Comparative Example 2]
A hydrogenated norbornene-based ring-opening copolymer was obtained in the same manner as in Example 1 except that 1,5-COD was changed to 30 mol% and MTF was changed to 70 mol%. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.

[Comparative Example 3]
A hydrogenated norbornene-based ring-opening copolymer was obtained in the same manner as in Example 1 except that the monocyclic monoene cyclopentene was changed to 8 mol% and MTF was changed to 92 mol% instead of the monocyclic nonconjugated polyene. The molecular weight, hydrogenation rate, glass transition temperature (Tg), melt flow rate (MI), bending strength, haze measurement, appearance inspection of molded products, and quality stability evaluation of hydrides of norbornene-based ring-opening copolymers It is shown in Table 1.

[Comparative Example 4]
Instead of the monocyclic non-conjugated polyene, 1,3-cyclooctadiene (hereinafter abbreviated as “1,3-COD”), which is a monocyclic conjugated polyene, was 6 mol%, and the MTF was 94 mol%. Except for the above, the polymerization reaction was carried out in the same manner as in Example 1. As a result, the polymerization did not proceed, and thus a hydride of a ring-opening copolymer could not be obtained. When the polymerization reaction solution was measured by gas chromatography, the monomer conversion rate was 0.2% for 1,3-COD and 1.4% for MTF.

  Although the polymerization reaction was further attempted 4 times in the same manner as in Example 1, the polymerization reaction did not proceed in any case. Monomer conversion is 0.2%, 0.1%, 0.4%, 0.2%, 0.1% for 1,3-COD, 1.4% for MTF, They were 0.9%, 1.8%, 1.1%, and 0.6%.

From this result, the following can be understood.
Unless a monocyclic non-conjugated polyene is copolymerized, the fluidity and strength are poor (Example 1, Comparative Example 1).
When the ratio of monocyclic nonconjugated polyene is too high, heat resistance will fall and it will be inferior to shaping | molding stability (Examples 1-4, Comparative Example 2).
When the monocyclic monoene is used, the strength decreases, the variation in the conversion rate to the polymer is large, the variation in Mw, Tg, MI, etc. is large and the quality stability is low (Examples 1 to 4, Comparative Example 3). ).
When a monocyclic conjugated polyene is used, polymerization does not proceed (Example 1, Comparative Example 4).
Therefore, it can be seen that the hydride of the norbornene-based ring-opening copolymer of the present invention provides an optical lens having an excellent balance of fluidity, heat resistance, transparency and strength, and high quality stability.

Claims (5)

A hydride of a norbornene-based ring-opening copolymer obtained by hydrogenating a norbornene-based ring-opening copolymer obtained by ring-opening polymerization of a monocyclic non-conjugated polyene and a norbornene-based monomer, A norbornene-based ring-opening copolymer hydride having a molar content ratio of a structural unit derived from a cyclic non-conjugated polyene and a structural unit derived from a norbornene-based monomer of 1/99 to 20/80. The norbornene-based ring-opening copolymer hydride according to claim 1, wherein the norbornene-based monomer contains 50 mol% or more of a tricyclic or more norbornene-based monomer. A molded article comprising the hydride of the norbornene-based ring-opening copolymer according to claim 1 or 2. An optical lens comprising the hydride of the norbornene-based ring-opening copolymer according to claim 1 or 2. The optical lens according to claim 4, wherein the optical lens is formed by injection molding.