JP2010150443A - Norbornene-based ring-opening polymer hydrogenated material and utilization of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a molded body having a small-size and thin lens shape excellent in optical characteristics and heat-resistance, with good moldability. <P>SOLUTION: The molded body is manufactured by using the norbornene-based ring-opening polymer hydrogenated material containing a repetition unit (A) originated from tetracyclododecene, of 20 to 70 mol% and a repetition unit (B) originated from methanotetrahydrofluorene, of 30 to 80 mol% in a molecule, wherein a weight-average molecular weight falls into the range of 20,000 to 40,000, and a peak area (a) of higher magnetic field side and a peak area (b) of lower magnetic field side, of methylene peak originated from methylene group in a six-membered ring structure originated from methanotetrahydrofluorene in<SP>13</SP>C-NMR spectrum measured in heavy chloroform (TMS standard) satisfy the relation of 0.7≤b/(a+b)≤1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymer and an optical resin material that provide a small thin molded article having excellent optical characteristics, and an optical molded article using the same.

As a transparent resin suitable for optical materials, thermoplastic norbornene polymers are widely known. Among them, in Patent Document 1, tetracyclo ^(9.2.1.0 2,10 ^{.0 3, 8)} tetradeca -3,5,7,12- tetraene methanolate tetrahydrofluorene having (methanolate tetrahydrofluorene) structure It has been disclosed that a hydrogenated product of a single ring-opening polymer of a compound gives a molded article excellent in transparency, low birefringence, oil and fat deterioration resistance, and heat resistance.
Tetracyclo ^(9.2.1.0 2,10 ^{.0 3, 8)} tetradeca -3,5,7,12- tetraene stereoisomers (end of the structural units derived from methanolate tetrahydrofluorene compound having a (meth Bruno tetrahydrofluorene) structure The composition ratio of -exo isomerism) has not been particularly focused on in the past, but in Patent Document 2, this composition ratio is controlled so that the end of the rubornene-based ring-opening polymer hydrogenated product having a (methanotetrahydrofluorene) structure is obtained. It is disclosed that by increasing the content of the shape, a molded body having improved heat resistance and small deformation under high humidity can be obtained.
In Patent Document 3, the number average molecular weight is 18,000 to 28,000 and the weight average molecular weight is 20,000 in order to further increase the mechanical strength of the molded product obtained from such a norbornene-based ring-opening polymer hydrogenated product. It has been proposed to control to ~ 42,000.

International Publication No. WO96 / 10596 International Publication No. WO99 / 09085 International Publication WO2005 / 080467

Based on this conventional technology, we studied to obtain a small and thin lens such as a camera lens mounted on a mobile phone by injection molding. When such a small molded body is injection-molded, the path through which the optical material is poured into the mold is also small. When an optical material containing a norbornene-based ring-opening polymer hydrogenated product (Examples 3 and 4) specifically described in Patent Document 3 is used in such a molding apparatus, transferability is deteriorated due to insufficient fluidity. Therefore, it was confirmed that molding defects occurred, and on the other hand, it was inferior in low birefringence due to orientation due to insufficient fluidity.
Therefore, as a result of intensive studies to obtain a compact, thin lens-shaped molded article excellent in optical characteristics and heat resistance with good moldability, the present inventors have found that 20 to 20 repeating units (A) derived from tetracyclododecene. In a norbornene-based ring-opening polymer hydrogenated product containing 70 mol% and a repeating unit (B) derived from methanotetrahydrofluorene in an amount of 30 to 80 mol%, stereoisomerism (endo-exo isomerism) of a structural unit derived from a methanotetrahydrofluorene compound Norbornene-based ring-opening polymer hydrogenated products whose composition ratio is controlled in the opposite manner to those proposed in Patent Documents 2 and 3, are excellent in thin-wall moldability and have high optical properties and heat resistance. Thus, the present inventors have found that a molded product balanced in the above can be obtained, and have completed the present invention.

Thus, according to the present invention, the norbornene system contains 20 to 70 mol% of the repeating unit (A) derived from tetracyclododecene and 30 to 80 mol% of the repeating unit (B) derived from methanotetrahydrofluorene in the molecule. a ring-opening polymer hydrogenation product, in a range of weight average molecular weight of 20,000 to 40,000, and sixth from methanolate tetrahydrofluorene in ¹³ C-NMR spectrum as measured in heavy chloroform (TMS standard) The peak area (a) on the high magnetic field side and the peak area (b) on the low magnetic field side of the methylene peak derived from the methylene group in the membered ring structure satisfy the relationship of the formula 0.7 ≦ b / (a + b) ≦ 1. A norbornene-based ring-opening polymer hydrogenated product is provided that satisfies the requirements. In addition, an optical resin material containing the hydrogenated norbornene-based ring-opening polymer and a compounding agent is provided, and an optical molded body obtained by molding the optical resin material is provided.

The hydrogenated norbornene-based ring-opening polymer of the present invention is derived from a methylene group in a six-membered ring structure derived from methanotetrahydrofluorene in a ¹³ C-NMR spectrum measured in deuterated chloroform (TMS (tetramethylsilane) standard). The peak area (A) on the high magnetic field side and the peak area (B) on the low magnetic field side of the methylene peak are in a relation of the formula 0.7 ≦ b / (a + b) ≦ 1.0. Among these, 0.75 ≦ b / (a + b) ≦ 1.0 is preferable, and 0.8 ≦ b / (a + b) ≦ 1.0 is more preferable. When the b / (a + b) value is within this range, the fluidity at the time of molding is improved and the thin-wall moldability is excellent.

^The methylene peak derived from the methylene group in the six-membered ring structure derived from methanotetrahydrofluorene measured by ¹³ C-NMR is split into two peaks due to the difference in the three-dimensional structure of the repeating unit derived from tetrahydrofuran. This difference in steric structure is due to the endo-exo isomerism of the repeating unit derived from the norbornene monomer.

Hydrogenation of a carbon-carbon unsaturated bond in a six-membered ring derived from methanotetrahydrofluorene newly produces a peak derived from a methylene group in the ring that does not exist in the polymer before hydrogenation, split into two. .
The calculated values (a) and (b) of the areas of these methylene peaks A and B are represented by the heights (Ha) and (Hb) of the respective integral curves (a) and (b). The
The calculation of the peak area may be performed by the method described in International Publication WO99 / 009085. That is, the area ratio between the peak area (a) on the high magnetic field side and the peak area (b) on the low magnetic field side of the methylene peak can be calculated by the calculation formula b / (a + b) = Hb / (Ha + Hb).

Ring-opened norbornene polymer hydrogenation product of the present invention, tetracyclododecene having tetracyclo ^(4.4.0.1 2, 5 ^{.1 7,10)} dodeca-3-ene (tetracyclododecene) structure a repeating unit (a) 20 to 70 mole% derived from tetracyclododecene provided by compounds, tetracyclo ^(9.2.1.0 2,10 ^{.0 3,8)} tetradeca -3,5,7,12- 30 to 80 mol% of a repeating unit (B) derived from methanotetrahydrofluorene provided by a methanotetrahydrofluorene compound having a tetraene (methanotetrahydrofluorene) structure. In the present invention, the norbornene-based ring-opening polymer hydrogenated product usually contains 10 mol% or less of other repeating units (C), as long as the repeating units (A) and (B) are within the above range. May be included at a ratio of 0.1 to 5 mol%. If the proportion of the repeating unit (A) is small, the heat resistance of the molded product is reduced and yellowing is likely to occur. Conversely, if the proportion of the repeating unit (A) is too large, the stability of the polymer in the solution is low (deposition However, it is difficult to produce the norbornene-based ring-opening polymer hydrogenated product itself.

The compound from which the repeating unit (C) is derived is not particularly limited, but tricyclo (4.3.0.12, from the good ring-opening polymerizability with a tetracyclododecene compound or a methanotetrahydrofluorene compound ^{. 5} ) Dicyclopentadiene compound having a deca-3,7-diene structure and other norbornene compounds having a bicyclo (2.2.1) hept-2-ene structure.
The tetrahydrofluorene compound, methanotetrahydrofluorene compound, norbornene compound, and dicyclopentadiene compound are all linear, branched or cyclic hydrocarbon groups having 1 to 6 carbon atoms, preferably alkyl groups having 1 to 3 carbon atoms, alkenyls. Group or an alkylidene group may be substituted.

Examples of the tetracyclododecene compound include 8-methyl-tetracyclo (4.4.0.1 ^2,5 . ^7,10 ) dodec-3-ene, 8-ethyl-tetracyclo (4.4.0.1 ^{2). , 5.1 7,10)} dodeca-3-ene, 8-ethylidene - tetracyclo ^(4.4.0.1 2, 5 ^{.1 7,10)} dodeca-3-ene, 8-vinyl - tetracyclo (4. 4.0.1 ^2,5 .1 ^7,10) dodeca-3-ene, 8-propenyl - tetracyclo ^(4.4.0.1 2,5 ^{.1 7,10)} dodeca-3-ene and the like It is done.
Methanolate The tetrahydrofluorene compound, tetracyclo ^(9.2.1.0 2,10 ^{.0 3,8)} tetradeca -3,5,7,12- tetraene (1,4-methano -1,4,4a, 9a - also referred tetrahydro -9H- fluorene), tetracyclo ^(8.4.14,7.0 1,10 ^{.0 3,8)} pentadeca -5,10,12,14- tetraene (1,4-methano-1, 4, 4a, also referred to as hexa hydro anthracene to 5,10,10a), 11- methyl - tetracyclo ^(9.2.1.0 2,10 ^{.0 3,8)} tetradeca -3,5,7,12- And tetraene (1,4-methano-4-methyl-1,4,4a, 9a-tetrahydro-9H-fluorene).

Dicyclopentadiene compounds include tricyclo (4.3.0.1 ^2,5 ) deca-3,7-diene (common name: dicyclopentadiene), methyl dicyclopentadiene, dimethyl dicyclopentadiene, ethyl dicyclopentadiene, Examples thereof include vinyl dicyclopentadiene and propenyl dicyclopentadiene.

  Other norbornene compounds include, for example, bicyclo (2.2.1) hept-2-ene (2-norbornene), 5-methyl-bicyclo (2.2.1) hept-2-ene (5-methyl- 2-norbornene), 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-decyl-bicyclo (2.2.1) hept-2-ene, 5-cyclohexyl-bicyclo (2.2.1) hept-2-ene, 5-cyclopentyl-bicyclo (2.2.1) norbornenes having an alkyl group such as hept-2-ene; 5-ethylidene-bicyclo (2.2.1) hept-2-ene (5-ethylidene-2-norbornene), 5- Vinyl-bicyclo 2.2.1) Hept-2-ene, 5-propenyl-bicyclo (2.2.1) hept-2-ene, 5-cyclohexenyl-bicyclo (2.2.1) hept-2-ene, 5 Norbornenes having an alkenyl group such as cyclopentenyl-bicyclo (2.2.1) hept-2-ene; 5-phenyl-bicyclo (2.2.1) hept-2-ene (5-phenyl-2- Norbornenes having an aromatic ring such as norbornene); 5-methoxycarbonyl-bicyclo (2.2.1) hept-2-ene (5-methoxycarbonyl-2-norbornene), 5-ethoxycarbonyl-5-methyl-bicyclo (2.2.1) Hept-2-ene, 2-methylpropionic acid 5-hydroxy-bicyclo (2.2.1) hept-2-ene, 5,6-di (hydroxymethyl) -bi Chlo (2.2.1) hept-2-ene, 5-hydroxyisopropyl-bicyclo (2.2.1) hept-2-ene, 5,6-dicarboxy-bicyclo (2.2.1) hept- Norbornenes having a polar group containing an oxygen atom such as 2-ene, 6-carboxy-5-methoxycarbonyl-bicyclo (2.2.1) hept-2-ene; 5-cyano-bicyclo (2.2.1) ) Norbornenes having a polar group containing a nitrogen atom such as hept-2-ene and 6-carboxy-5-cyano-bicyclo (2.2.1) hept-2-ene;

  These compounds (hereinafter collectively referred to as “norbornene monomers”) are subjected to ring-opening polymerization, and then hydrogenated to obtain the hydrogenated norbornene-based ring-opening polymer of the present invention. By setting the hydrogenation reaction conditions to the special conditions described later, the peak area on the high magnetic field side (A) and the peak area on the low magnetic field side of the methylene peak derived from the methylene group in the six-membered ring structure derived from methanotetrahydrofluorene ( B) can be easily controlled within the above range.

  The ring-opening polymerization of the norbornene-based monomer is usually −20 to + 100 ° C., preferably 10 to 80 ° C., usually 0 to 5 MPa, preferably 0 to 2 MPa, and usually 30 minutes to 20 hours, preferably 1 to 10 hours using a metathesis polymerization catalyst. As the metathesis polymerization catalyst, a catalyst composed essentially of (a) a transition metal compound catalyst component, (b) a metal compound co-catalyst component, and (c) a third component for increasing the polymerization activity as necessary is suitably employed. However, there is no particular limitation as long as it is a catalyst used as a metathesis polymerization catalyst. The ring-opening polymerization can be carried out without a solvent, but is preferably carried out in a suitable solvent. The organic solvent to be used is not particularly limited as long as the polymer and the polymer hydrogenated product are dissolved or dispersed under predetermined conditions and do not affect the polymerization and hydrogenation. (Aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons and ethers) are preferred. In the ring-opening polymerization, a molecular weight regulator such as α-olefin can be added to the reaction system. The molecular weight of the resulting ring-opening polymer can be adjusted by adding a molecular weight regulator.

Hydrogenation can be carried out by bringing the ring-opened polymer into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. Hydrogenation is performed until 99% or more of the copolymer main chain is hydrogenated. Examples of the hydrogenation catalyst include JP-A-58-43412, JP-A-60-26024, JP-A-64-24826, JP-A-1-138257, and JP-A-7-41550. What is described can be used.
The catalyst may be homogeneous or heterogeneous. Homogeneous catalysts are easy to disperse in the hydrogenation reaction solution, so the addition amount may be small, and since they are active without high temperature and high 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, Rh or the like is supported on a carrier. In particular, when 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-based solvent is usually used because of the excellent solubility of the resulting hydrogenated product.
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 cyclohexane 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.

As the hydrogenation reaction conditions, at least the reaction temperature, the reaction hydrogen pressure, the reaction time, and the amount of the hydrogenation catalyst are selected in the following ranges in order to satisfy the above formula 0.7 ≦ b / (a + b) ≦ 1.
The reaction temperature is usually 180 to 280 ° C, preferably 180 to 260 ° C, more preferably 180 to 250 ° C. The reaction hydrogen pressure is usually 1.0 to 10 MPa, preferably 1.0 to 8.0 MPa, and more preferably 1.0 to 6.0 MPa. The time for the hydrogenation reaction is usually 1 to 50 hours, preferably 1 to 40 hours, and more preferably 1 to 30 hours. The amount of catalyst for hydrogenation is usually 0.1 to 30 g, preferably 1.0 to 25 g, more preferably 2.0 to 20 g, based on 100 g of the ring-opening polymer.

Among the above reaction conditions, particularly with respect to the reaction temperature, reaction hydrogen pressure, and reaction time, the hydrogenation reaction is performed under the reaction conditions satisfying the following (A), and then the hydrogenation reaction is performed under the reaction conditions satisfying (B). Is preferable in order to satisfy the formula 0.7 ≦ b / (a + b) ≦ 1.
In the step (A), b / (a + b) of the obtained resin composition can be easily within the range of the present invention, and the step (B) can further increase the hydrogenation rate of the obtained resin composition. it can.

(A): The reaction temperature is preferably 180 to 250 ° C., more preferably 200 to 250 ° C., the reaction hydrogen pressure is preferably 1.0 to 3.0 MPa, more preferably 1.0 to 2.5 MPa, and the reaction time is Preferably it is 1 to 20 hours, more preferably 3 to 15 hours.
(B): The reaction temperature is preferably 180 to 250 ° C., more preferably 200 to 250 ° C., the reaction hydrogen pressure is preferably 4.0 to 6.0 MPa, more preferably 4.5 to 6.0 MPa, and the reaction time is Preferably it is 1 to 20 hours, more preferably 3 to 15 hours.

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.
For the purpose of suppressing the elution of the remaining transition metal, an adsorbent such as alumina having a specific pore volume and specific surface area as disclosed in JP-A-5-317411, etc., or a resin is used. The solution can be washed 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 hydrogenation rate of the carbon-carbon double bond and the aromatic ring of the main chain of the hydrogenated norbornene-based ring-opening polymer of the present invention thus obtained is preferably a value calculated from a ¹ H-NMR spectrum. Is 97% or more, more preferably 99% or more, and most preferably 99.9% or more. More highly hydrogenated polymers can measure the hydrogenation rate of the main chain and cyclic hydrocarbon structure in GPC measurement using cyclohexane as a solvent, and the peak detected by the UV-visible detector of GPC The smaller the (UV / RI) calculated from the area (UV) and the peak area (RI) detected by the differential refractometer, the fewer residual double bonds and the higher the hydrogenation rate. (UV / RI) is preferably 1.0 or less, more preferably 0.8 or less, and most preferably 0.5 or less.

The weight average molecular weight (Mw) of the hydrogenated norbornene-based ring-opening polymer of the present invention thus obtained is 20,000 to 40,000, preferably 23,000 to 40,000, more preferably It is 2,3,000 to 3,8000, particularly preferably 2,5,000 to 3,8,000. As the weight average molecular weight increases, the mechanical strength tends to increase. However, if the weight average molecular weight is too large, not only the moldability decreases, but also the birefringence of the molded product due to the orientation during molding increases and the optical properties deteriorate. To do. On the other hand, if the weight average molecular weight is too small, the strength of the molded article is insufficient.
Although the method of making a weight average molecular weight into the said range is not limited, For example, it can adjust with the above-mentioned chain transfer agent. The addition amount of the chain transfer agent is appropriately adjusted according to various conditions such as polymerization catalyst species, polymerization catalyst amount, monomer species, monomer amount, chain transfer agent, etc. Generally, when the addition amount is large, the weight average molecular weight is increased. On the contrary, if the amount added is small, the weight average molecular weight increases.
Moreover, molecular weight distribution (MWD = Mw / Mn) becomes like this. Preferably it is 1.0-3.0, More preferably, it is 1.0-2.5, More preferably, it is 1.0-2.0.
When the molecular weight distribution is in this range, it is preferable because the thin-wall moldability is excellent and the mechanical strength of the molded body can be secured. In addition, Mn is a number average molecular weight measured by gel permeation chromatography (GPC) like Mw.

  The glass transition temperature (Tg) based on JIS K 6911 of the norbornene-based ring-opening polymer hydrogenated product of the present invention is usually 120 to 170 ° C., preferably 125 to 170 ° C., more preferably 130 to 170 ° C.

  The melt flow rate of 280 ° C. and a load of 2.16 kgf, measured based on JIS K 6719 of the norbornene-based ring-opening polymer hydrogenated product of the present invention, is usually 25 to 150 (g / 10 min), preferably 30 to 100 (g / 10 min), more preferably 30 to 60. This is a norbornene-based ring-opening polymer hydrogenated product containing 20 to 70 mol% of the repeating unit (A) derived from tetracyclododecene and 30 to 80 mol% of the repeating unit (B) derived from methanotetrahydrofluorene. This is achieved by satisfying the relationship of the above formula 0.7 ≦ b / (a + b) ≦ 1 and controlling the weight average molecular weight in the range of 20,000 to 40,000.

Various compounding agents can be blended in the norbornene-based ring-opening polymer hydrogenated product used in the present invention, if necessary.
Examples of the compounding agent include an antioxidant, an ultraviolet absorber, a weather resistance stabilizer, an antistatic agent, a release agent, and a polymer having a glass transition temperature of 40 ° C. or lower. These compounding agents can be used singly or in combination of two or more, but the compounding amount is usually 0 with respect to 100 parts by weight of the norbornene-based ring-opening polymer hydrogenated product in consideration of optical characteristics. 0.005 to 5 parts by weight, preferably 0.005 to 2 parts by weight, more preferably 0.005 to 1 part by weight.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like. Examples of the ultraviolet absorber include a benzotriazole ultraviolet absorber, a benzoate ultraviolet absorber, a benzophenone ultraviolet absorber, an acrylate ultraviolet absorber, and a metal complex ultraviolet absorber.
Examples of the light stabilizer include hindered amine light stabilizers.

  Near-infrared absorbers include, for example, cyanine-based near-infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; Complex near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers;

A polymer having a glass transition temperature of 40 ° C. or lower is preferably used because it can highly prevent white turbidity of the molded body under constant temperature and high humidity conditions. Rubbery polymers include rubber and thermoplastic elastomers. When there are two or more glass transition temperatures as in the block copolymer, the glass transition temperature can be used as a rubbery polymer if the lowest glass transition temperature is 40 ° C. or lower. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the rubbery polymer is appropriately selected according to the purpose of use, but is usually 5 to 300.

  Examples of rubber polymers include ethylene-α-olefin rubbers; ethylene-α-olefin-polyene copolymer rubbers; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Polymer: Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate copolymer; alkyl acrylate such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. Polymer: Polybutadiene, polyisoprene, random copolymer of styrene and butadiene or isoprene, acrylonitrile-butadiene copolymer, butadiene-isoprene copolymer, butadiene- (meth) acrylic acid alkyl ester copolymer, butadiene- ( Meta) Diene rubbers such as alkyl acrylate-acrylonitrile copolymer and butadiene- (meth) acrylic acid alkyl ester-acrylonitrile-styrene copolymer; butylene-isoprene copolymer; styrene-butadiene block copolymer, hydrogenated styrene -Aromatic vinyl-conjugated diene block copolymers such as butadiene block copolymer, hydrogenated styrene-butadiene random copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, low crystal And polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene ionomer resins.

After adding various compounding agents to the norbornene-based ring-opening polymer hydrogenated product as necessary, it is usually pelletized and subjected to molding.
Specifically, the norbornene-based ring-opening polymer hydrogenated product and the compounding agent are melted, and a known kneading apparatus such as an open mixing roll, a non-open Banbury mixer, a pressure kneader, or a continuous mixer is used. After kneading, pelletize using a pelletizer. The kneading temperature is preferably in the range of 180 to 400 ° C, and more preferably in the range of 200 to 350 ° C. In addition, when kneading, the components may be added together and kneaded or may be kneaded while being added in several times.

Although there is no particular limitation on the method of molding a lens using this pellet, an injection molding method is usually employed. The molding conditions are not particularly limited, but the resin temperature during molding is usually 200 ° C to 400 ° C, preferably 210 ° C to 350 ° C. The mold temperature t ₀ ° C. is usually room temperature <t ₀ <(t ₁ +15) ° C., preferably (t ₁ ), where the glass transition temperature of the norbornene-based ring-opening polymer hydrogenated product used is t ₁ ° C. −30) <t ₀ <(t ₁ +10) ° C., more preferably (t ₁ −20) <t ₀ <(t ₁ +5) ° C. (where (t ₁ −30) <room temperature, or ( (t ₁ -20) If room temperature <room temperature, room temperature <t ₀ ° C.) It is preferable that the resin temperature and the mold temperature at the time of molding are in this range in terms of releasability between the mold and the lens as the molded body.

Of the optically molded products thus obtained, the norbornene-based ring-opening polymer hydrogenated product of the present invention can be suitably used for small thin lenses and the like. Such an optical molded body can be annealed as desired. Thereby, it is possible to sharpen the refractive index distribution of the molded body. In the annealing process, heat treatment is performed at 80 to 110 ° C. for 5 to 24 hours after molding.
Also, a hard coat layer made of inorganic compounds, organic silicon compounds such as silane coupling agents, acrylic resins, vinyl resins, melamine resins, epoxy resins, fluorine resins, silicone resins, etc. is formed on the surface of the optical molded body. can do. When the hard coat layer is formed, the heat resistance, optical properties, chemical resistance, abrasion resistance, water resistance, and the like of the molded body can be improved. Examples of the method for forming the hard coat layer include known methods such as a thermal curing method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method.

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), and the molecular weight distribution (MWD) were measured as standard polyisoprene equivalent 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 as a column in series, 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 (carbon-carbon double bond residual rate)
The hydrogenation rate of the main chain and cyclic hydrocarbon structure in the norbornene-based ring-opening polymer is detected by a GPC UV-visible detector in gel permeation chromatography (GPC) measurement using cyclohexane as a solvent. (UV / RI) was calculated from the peak area (UV) and the peak area (RI) detected by a differential refractometer, and the value was evaluated. A smaller (UV / RI) indicates a lower residual double bond and a higher hydrogenation rate.

(3) Glass transition temperature (Tg)
Tg was measured based on JIS K 6911 using a differential scanning calorimeter.

(4) Melt flow rate (MI)
MI was measured based on JIS K 6719 at 280 ° C. and a load of 2.16 kgf.

(5) Thin-wall moldability Thin-wall moldability includes a convex radius of curvature of 5.73 mm, a concave radius of curvature of 3.01 mm, a diameter of 4.5 mm, a lens portion diameter of 3 mm, and a lens center thickness of 0. Using a mold for forming a lens of 2 mm, a molded product was produced by injection molding. About the obtained molded article, both sides were scanned in the range of 2 mm in diameter from the center with a non-contact three-dimensional measuring device (manufactured by Mitaka Kouki Co., Ltd .; product name “NH-3SP”), and the approximate radius of curvature was calculated. A deviation between the calculated approximate radius of curvature of the molded product and the radius of curvature of the mold design value was obtained, and a value (PV value (μm)) obtained by subtracting the minimum value from the maximum value of the deviation was calculated. The smaller the PV value, the better the mold transferability.

(6) Mechanical strength The mechanical strength of the norbornene-based polymer is based on ASTM D790 using resin plate A (length 10 cm × width 1 cm × thickness 1 mm), fulcrum distance 30.0 mm, pressure 30 MPa, The bending strength was measured using Autograph AGS-10kND manufactured by Shimadzu Corporation under the conditions of Method A, temperature 23 ° C., humidity 50%, and 40 hours after molding. The larger the bending strength, the better. If it is small, the molded body will crack during molding.

(7) Birefringence (retardation value)
The birefringence of the norbornene-based ring-opening polymer hydrogenated product is measured with a birefringence meter (manufactured by Oji Scientific Instruments: KOBRA-CCD / X) using a resin plate B (length 60 mm × width 60 mm × thickness 2 mm). Then, comparison was made according to the retardation value at the measurement wavelength of 650 nm at the center of the resin plate. The smaller the retardation value is, the better the low birefringence is. When it is 200 or less, the low birefringence is excellent, and when it is 100 or less, the low birefringence is particularly excellent.

(8) Heat resistance test yellowing The heat resistance test yellowing was performed using the molded body prepared in (5) above as a test piece, and the yellowness (YI: yellow index) of the test piece was measured according to JIS K 7103 using a color difference meter. Was measured as air, and a value obtained by subtracting the yellowness YI of only air from the measured yellowness YI was obtained as a yellowness difference ΔYI (measurement was performed three times and the average value was used), (5) The molded body produced in (1) was placed in an oven at 100 ° C., and ΔYI of the molded body after 400 hours was measured. It shows that it is excellent in heat-resistant yellowing, so that the value of (DELTA) YI is small.

Example 1
Dried and purged with nitrogen polymerization reactor, tetracyclo ^(9.2.1.0 2,10 ^{.0 3, 8)} tetradeca -3,5,7,12- tetraene (hereinafter, MTF hereinafter) 60 mol% , tetracyclo ^(4.4.0.1 2, 5 ^{.1 7,10)} dodeca-3-ene (hereinafter, TCD hereinafter) monomer mixture 7 parts of 40 mol% (to the total amount of monomers used in the polymerization 1%), dehydrated cyclohexane 1500 parts, molecular weight regulator 3.8 parts 1-hexene 1.3 parts diisopropyl ether 0.33 parts isobutyl alcohol 0.84 parts triisobutylaluminum and hexachloride 35 parts of a 0.66% tungsten cyclohexane solution was added and stirred at 55 ° C. for 10 minutes. Next, while maintaining the reaction system at 55 ° C. and stirring, 693 parts of the monomer mixture and 52 parts of a tungsten hexachloride 0.66% cyclohexane solution are continuously dropped into the polymerization reactor over 150 minutes. 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 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 18 parts of a diatomaceous earth-supported nickel catalyst (nickel support rate: 58% by weight) were added. After replacing the inside of the autoclave with hydrogen, the reaction was carried out at 220 ° C. under a hydrogen pressure of 2.5 MPa for 6 hours, and then the hydrogen pressure was raised to 4.5 MPa and reacted for 6 hours. After completion of the hydrogenation reaction, radiolight # 500 was used as a filter bed, and a pressure filter (Honda filter manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) was used, and pressure filtration was performed at a pressure of 0.25 MPa to obtain a colorless and transparent solution. . Next, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (product name) as an antioxidant per 100 parts of the hydrogenated product was added to the resulting solution. 0.5 parts of “Irganox 1010” (manufactured by Ciba Specialty Chemicals) were added and dissolved.

  After filtering this solution with a zeta plus filter 30H (pore size 0.5 to 1 μm, manufactured by Cuno filter), the filtrate was filtered with a metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Corp.) to remove foreign matters. Removed.

Next, the filtrate obtained above was concentrated using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.) at a temperature of 280 ° C. and a pressure of 1 kPa or less to remove cyclohexane and other volatile components as solvents from the solution. Extruded into a strand in a molten state from a die directly connected to the machine, cooled with water, and then cut with a pelletizer (model number “OSP-2”, manufactured by Nagata Seisakusho) to obtain pellets of a ring-opened polymer hydrogenated product.
This norbornene-based ring-opening polymer hydrogenated product was subjected to a peak area on the high magnetic field side (21 to 21.5 ppm) of a methylene peak derived from a methylene group in a six-membered ring structure derived from methanotetrahydrofluorene in a ¹³ C-NMR spectrum. The area ratio b / (a + b) between (a) and the peak area (b) on the low magnetic field side (21.5 to 22 ppm) was 0.77.
The molecular weight of this ring-opening polymer hydrogenated product is Mw = 29,800, Mn = 17,000, MWD = 1.75, the hydrogenation rate (UV / RI) is 0.12, and the glass transition temperature (Tg). Was 137 ° C. and the melt flow rate (MI) was 45 (g / 10 min).
This pellet is formed into a concave meniscus lens having a convex curvature radius of 5.73 mm, a concave curvature radius of 3.01 mm, a size of 4.5 mm, a lens portion diameter of 3 mm, and a lens center thickness of 0.2 mm. Using a mold for forming, a lens was obtained by injection molding under the conditions of a cylinder temperature of 290 ° C., a mold temperature of 125 ° C., an injection speed of 10 mm / second, a holding pressure of 30 MPa, and a back pressure of 5 MPa. The resulting lens was evaluated for thin-wall formation and heat resistance test yellowing. ΔYI after the heat test was 2.3. The results are shown in Table 1.
The pellets were subjected to an injection molding machine (product name “Roboshot α-100B”, manufactured by FANUC) at a resin temperature of 280 ° C., a mold temperature of 130 ° C., and an injection pressure of 100 MPa, a length of 10 cm × width of 1 cm × thickness of 1 mm. The resin plate A and a resin plate B having a length of 60 mm × width of 60 mm × thickness of 2 mm were prepared, the mechanical strength was measured using the resin plate A, and the birefringence was measured using the resin plate B. The mechanical strength was 96 MPa, and the retardation (Re) value was 98 nm.

(Example 2)
A ring-opened polymer hydrogenated product was obtained in the same manner as in Example 1 except that the composition of the monomer mixture was MTF 40 mol% and TCD 60 mol%.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.75, the molecular weight is Mw = 31,100, Mn = 17,400, and MWD = 1.79. The hydrogenation rate was (UV / RI) 0.14, Tg 138 ° C., and MI 41 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 2.1, the mechanical strength was 115 MPa, and the value of retardation (Re) was 121 nm. The results are shown in Table 1.

(Example 3)
A hydrogenated ring-opening polymer was obtained in the same manner as in Example 1 except that the composition of the monomer mixture was MTF 80 mol% and TCD 20 mol%.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.81, the molecular weight is Mw = 29,200, Mn = 17,200, and MWD = 1.70. The hydrogenation rate was 0.22 for (UV / RI), 134 ° C. for Tg, and 46 (g / 10 min) for MI.
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 2.7, the mechanical strength was 81 MPa, and the value of retardation (Re) was 111 nm. The results are shown in Table 1.

Example 4
A ring-opening polymer hydrogenated product was obtained in the same manner as in Example 1 except that 3.3 parts of 1-hexene was used.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.75, the molecular weight is Mw = 35,200, Mn = 23,100, and MWD = 1.52. The hydrogenation rate (UV / RI) was 0.18, Tg was 140 ° C., and MI was 39 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 2.2, the mechanical strength was 110 MPa, and the value of retardation (Re) was 109 nm. The results are shown in Table 1.

(Example 5)
18 parts of an alumina-supported nickel catalyst (nickel support ratio 35% by weight) is added to the catalyst and reacted at a reaction temperature of 230 ° C. under a hydrogen pressure of 2.0 MPa for 6 hours, and then at a hydrogen pressure of 4.5 MPa for 6 hours. A ring-opening polymer hydrogenated product was obtained in the same manner as in Example 1 except that
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.76, the molecular weight is Mw = 30,100, Mn = 17,100, and MWD = 1.76. The hydrogenation rate (UV / RI) was 0.19, Tg was 137 ° C., and MI was 44 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, heat resistance test yellowing, mechanical strength, and birefringence. ΔYI after the heat test was 2.5, the mechanical strength was 99 MPa, and the value of retardation (Re) was 99 nm. The results are shown in Table 1.

(Comparative Example 1)
The ring-opened polymer hydrogenated product was the same as in Example 1 except that the amount of the diatomaceous earth-supported nickel catalyst was changed to 7 parts and the hydrogenation reaction was carried out at a reaction temperature of 180 ° C. and a hydrogen pressure of 4.5 MPa for 8 hours. Got.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.15, the molecular weight is Mw = 34,800, Mn = 2,600, MWD = 1.54, The hydrogenation rate was (UV / RI) 0.21, Tg was 163 ° C., and MI was 6 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 1.9, the mechanical strength was 126 MPa, and the value of retardation (Re) was 242 nm. The results are shown in Table 1.

(Comparative Example 2)
A ring-opening polymer hydrogenated product was obtained in the same manner as in Comparative Example 1 except that 4.1 part of 1-hexene was used.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.17, the molecular weight is Mw = 31,900, Mn = 19000, MWD = 1.68, The hydrogenation rate was (UV / RI) 0.20, Tg 162 ° C., and MI 20 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 1.9, the mechanical strength was 119 MPa, and the retardation (Re) value was 208 nm. The results are shown in Table 1.

(Comparative Example 3)
Example except that 9 parts of alumina-supported nickel catalyst (N163A, manufactured by JGC Chemical Co., Ltd.) was added instead of diatomaceous earth-supported nickel catalyst and the reaction temperature was 230 ° C. and a hydrogen pressure of 4.5 MPa for 8 hours. In the same manner as in Example 1, a ring-opened polymer hydrogenated product was obtained.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.43, the molecular weight is Mw = 32,200, Mn = 20,100, and MWD = 1.60. The hydrogenation rate was 0.31 for (UV / RI), 145 ° C. for Tg, and 27 (g / 10 min) for MI.
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, the heat resistance test yellowing, the mechanical strength, and the birefringence. ΔYI after the heat test was 3.9, the mechanical strength was 117 MPa, and the retardation (Re) value was 164 nm. The results are shown in Table 1.

(Comparative Example 4)
A hydrogenated ring-opening polymer was obtained in the same manner as in Example 1 except that the composition of the monomer mixture was MTF 100 mol%.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.77, the molecular weight is Mw = 30,500, Mn = 19000, MWD = 1.61. The hydrogenation rate (UV / RI) was 0.89, Tg was 137 ° C., and MI was 40 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, heat resistance test yellowing, mechanical strength, and birefringence. ΔYI after the heat test was 6.2, the mechanical strength was 60 MPa, and the value of retardation (Re) was 141 nm. The results are shown in Table 1.

(Comparative Example 5)
A ring-opened polymer hydrogenated product was obtained in the same manner as in Comparative Example 1 except that 1-hexene was changed to 2.9 parts.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.84, the molecular weight is Mw = 42,000, Mn = 21,000, MWD = 2.00, The hydrogenation rate (UV / RI) was 0.23, Tg was 139 ° C., and MI was 23 (g / 10 min).
Further, in the same manner as in Example 1, the obtained ring-opening polymer hydrogenated product was used to measure the thin-wall formability, heat resistance test yellowing, mechanical strength, and birefringence. ΔYI after the heat test was 2.6, the mechanical strength was 132 MPa, and the retardation (Re) value was 185 nm. The results are shown in Table 1.

(Comparative Example 6)
A ring-opened polymer hydrogenated product was obtained in the same manner as in Comparative Example 1 except that 5.3 parts of 1-hexene was used.
The addition ratio of the monomer of the polymerization reaction solution to the polymer was 99.9%. The peak area ratio b / (a + b) of the hydrogenated ring-opening polymer obtained by hydrogenation is 0.85, the molecular weights are Mw = 19000, Mn = 1800, MWD = 1.76, The hydrogenation rate (UV / RI) was 0.11, Tg was 134 ° C., and MI was 180 (g / 10 min).
Further, in the same manner as in Example 1, mechanical strength and birefringence were measured using the obtained ring-opening polymer hydrogenated product. The mechanical strength was 52 MPa, and the retardation (Re) value was 92 nm. The results are shown in Table 1. However, in the lens molding, since the lens is cracked and a normal lens cannot be obtained, the thin moldability and the heat resistance test yellowing measurement are not performed.

From this result, the ratio of the repeating unit derived from tetracyclododecene and the repeating unit derived from methanotetrahydrofluorene, the weight average molecular weight, and the methylene peak derived from the methylene group in the six-membered ring structure derived from methanotetrahydrofluorene on the high magnetic field side. The norbornene-based ring-opening polymer hydrogenated product in which the area ratio b / (a + b) of the peak area (a) and the peak area (b) on the low magnetic field side is within the range defined in the present invention is excellent in thin-wall moldability, It can be seen that the optical properties and mechanical strength of the molded body using this are also highly balanced (Examples 1 to 5).
On the other hand, the norbornene-based ring-opening polymer hydrogenated product in which the formula b / (a + b) is too small is inferior in thin-wall moldability, and a molded product using this is inferior in low birefringence ( Comparative Examples 1-3).
Moreover, it turns out that the molded object using the norbornene-type ring-opening polymer hydrogenated substance which does not contain the repeating unit derived from tetracyclododecene is inferior to heat-resistant yellowing (Comparative Example 4).
Furthermore, it can be seen that the hydrogenated norbornene-based ring-opening polymer having an excessively high weight average molecular weight has poor thin-wall moldability, and a molded product using this has poor low birefringence (Comparative Example 5). A norbornene-based ring-opening polymer hydrogenated product having a weight average molecular weight that is too small is inferior in thin-wall moldability, and a molded product using this has low mechanical strength (Comparative Example 6).

Claims (2)

Norbornene-based ring-opening polymer hydrogenated product containing 20 to 70 mol% of repeating units (A) derived from tetracyclododecene and 30 to 80 mol% of repeating units (B) derived from methanotetrahydrofluorene in the molecule A methylene group in a six-membered ring structure derived from methanotetrahydrofluorene in a ¹³ C-NMR spectrum having a weight average molecular weight in the range of 20,000 to 40,000 and measured in deuterated chloroform (TMS standard) The peak area (a) on the high magnetic field side and the peak area (b) on the low magnetic field side of the methylene peak derived from the above satisfy the relationship of 0.7 ≦ b / (a + b) ≦ 1 Norbornene-based ring-opening polymer hydrogenated product. An optical molded body obtained by molding the hydrogenated norbornene-based ring-opening polymer according to claim 1.