JP2013124310A - Alicyclic structure-containing polymer composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alicyclic structure-containing polymer composition excellent in transparency and high-temperature and high-humidity resistance, which is suitable for an optical molded article.SOLUTION: The alicyclic structure-containing polymer composition includes, relative to [A] 100 pts.wt. of an alicyclic structure-containing polymer; [B] 1-15 pts.wt. of a terpene phenol resin and [C] 0.05-0.5 pt.wt. of a soft polymer. The composition can be suitably used for an optical lens having a thickness of 0.1 mm or more.

Description

  The present invention provides an alicyclic structure-containing polymer composition excellent in transparency and high-temperature and high-humidity resistance, suitable for an optical molded body.

The alicyclic structure-containing polymer is excellent in transparency, low moisture absorption, chemical resistance, and heat resistance, and is used for optical members such as lenses and optical disk substrates. However, a molded body composed only of an alicyclic structure-containing polymer may become cloudy (inferior in high-temperature and high-humidity resistance) if it is placed in a high-temperature and high-humidity environment for a long time and then suddenly placed at room temperature. is there. Thus, attempts have been made to improve high temperature and high humidity resistance by adding a compounding agent to the alicyclic structure-containing polymer. For example, in Patent Document 1, transparency and the alicyclic structure-containing polymer are blended with a soft polymer such as a styrene-butadiene-styrene block copolymer that is incompatible with the alicyclic structure-containing polymer. It is disclosed that high temperature and high humidity resistance is improved. Further, in Patent Document 2, by using a soft polymer such as a styrene-butadiene-styrene block copolymer and a dipentaerythritol partial ester in combination, it is more transparent than in the case of a soft polymer alone even in a higher temperature and high humidity environment. And good resistance to high temperature and high humidity.
Patent Document 3 discloses that a resin composition having high transparency and wettability can be obtained by blending a terpene resin oligomer highly compatible with an alicyclic structure-containing polymer. 4 discloses that a material having high paintability and impact resistance can be obtained by blending a soft polymer in addition to an oligomer having an alicyclic structure and / or an aromatic cyclic structure such as a terpene resin oligomer. ing.

JP 2002-148401 A JP 2010-126673 A JP 2007-169578 A JP-A-8-230097

Resin lenses are easy to process and lightweight, so it is considered to apply resin lenses not only to small lenses such as pickup lenses, but also to large image lenses such as projector lenses and camera lenses. ing. The image lens is required to be a large lens having no transparency and excellent transparency.
However, if the resin composition containing the alicyclic structure-containing polymer and the soft polymer described in Patent Documents 1 and 2 can be used, the cloudiness of the small lens under a high humidity condition of 85 ° C. can be prevented. It has been found that a certain large image lens is slightly cloudy and cannot be prevented.
In addition, when the terpene resin oligomer proposed in Patent Document 3 is blended, the transparency at the time of molding is excellent, but a large amount of microcracks occur in a high temperature and high humidity environment, and the appearance and transparency are poor. I found out that And, as proposed in Patent Document 4, when a soft polymer is further added, the paintability and impact resistance are improved, but even in the case of a constant temperature and humidity environment and a small lens, the transparency is low. It turned out that it cannot be used as an optical lens.
An object of the present invention is to provide a resin composition that is more excellent in transparency and high temperature and humidity resistance and a molded body using the same, in view of the above situation.

  Thus, according to the present invention, 1 to 15 parts by weight of [B] terpene phenol resin and 0.05 to 0. 0. An alicyclic structure-containing polymer composition containing 5 parts by weight is provided. This composition is suitable for an optical molded material, and particularly suitable for an optical lens having a thickness of 0.1 mm or more.

<Aricyclic structure-containing polymer>
The alicyclic structure-containing polymer used in the present invention is an amorphous resin (resin having no melting point) having an alicyclic structure in the main chain and / or side chain, and has mechanical strength, heat resistance, etc. From the viewpoint, those containing an alicyclic structure in the main chain are preferred.

  Examples of the alicyclic structure of the polymer include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength, heat resistance, and the like, A cycloalkene structure is preferable, and among them, one having a cycloalkane structure is most preferable.

  The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, more preferably 5 to 15 in the range of mechanical strength and heat resistance. The properties of the properties and moldability are highly balanced and suitable.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight or more. More preferably, it is 70% by weight. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is excessively small, the heat resistance is inferior, which is not preferable. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is not particularly limited and is appropriately selected according to the purpose of use.

  Specific examples of the alicyclic structure-containing polymer include (1) norbornene-based polymer, (2) monocyclic olefin-based polymer, (3) cyclic conjugated diene-based polymer, and (4) vinyl alicyclic. Examples thereof include hydrocarbon polymers and hydrides (1) to (4). Among these, norbornene-based polymers and hydrides thereof are preferable from the viewpoints of heat resistance, mechanical strength, and the like.

(1) Norbornene-based polymer The norbornene-based polymer is obtained by polymerizing a norbornene-based monomer that is a monomer having a norbornene skeleton, and is obtained by ring-opening polymerization or by addition polymerization. Broadly divided into things.

As ring-opening polymerization, ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization, and hydrogens thereof. And the like. Examples of the polymers obtained by addition polymerization include addition polymers of norbornene monomers and addition polymers of norbornene monomers and other monomers copolymerizable therewith. Among these, a ring-opening polymer hydride of a norbornene-based monomer is preferable from the viewpoint of heat resistance, mechanical strength, and the like, and in particular, 7,8-benzotricyclo [4.3.0.1 ^2,5 A ring-opening polymer hydride of a norbornene monomer using deca-3-ene as a norbornene monomer is preferable because it exhibits a remarkable effect on heat resistance. A ring-opening polymer hydride of a norbornene monomer using 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene as a norbornene monomer is a norbornene monomer. The proportion of 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene in the monomer is preferably 50% by weight or more, more preferably 70% by weight or more, and particularly preferably 85%. It is more than wt%.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having a substituent in the ring), tricyclo [4.3.0 ^1,6 . 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 (methano Tetrahydrofluorene: 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) and its derivatives.
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.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymerization. It can be obtained by polymerization in the presence of a catalyst. Examples of the ring-opening polymerization catalyst include a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent, or a metal halide or acetylacetone such as titanium, zirconium, tungsten, or molybdenum. A catalyst comprising a compound and an organoaluminum compound can be used.
Examples of the other monomer capable of ring-opening copolymerization with a norbornene monomer include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.
The ring-opening polymer hydride of a norbornene-based monomer is usually obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the above-described ring-opening polymer, and then adding a carbon-carbon unsaturated bond. Can be obtained by hydrogenation.

  An addition polymer of a norbornene monomer, or an addition polymer of a norbornene monomer and another monomer copolymerizable therewith, these monomers are added to a known addition polymerization catalyst, for example, It can be obtained by polymerization using a catalyst comprising a titanium, zirconium or vanadium compound and an organoaluminum compound.

Examples of other monomers that can be addition copolymerized with norbornene-based monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and the like. derivatives; cyclobutene, cyclopentene, cyclohexene, cyclooctene, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] cyclodeca-3,5,7,12-tetraene (also referred to as 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene), and derivatives thereof; 1 , 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, non-conjugated dienes such as 1,7-octadiene, and the like. Among these, α-olefins are preferable and ethylene is particularly preferable.
These other monomers capable of addition copolymerization with norbornene monomers can be used alone or in combination of two or more. In the case of addition copolymerization of a norbornene monomer and another monomer capable of addition copolymerization, other units capable of addition copolymerization with the structural unit derived from the norbornene monomer in the addition polymer. Appropriately, the ratio with the structural unit derived from the monomer is usually in the range of 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5 by weight. Selected.

(2) Monocyclic cyclic olefin polymer As the monocyclic olefin polymer, for example, an addition polymer of a monocyclic olefin monomer such as cyclohexene, cycloheptene, or cyclooctene can be used. it can.
(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and The hydride can be used.
(4) Vinyl alicyclic hydrocarbon polymer Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinyl cyclohexene and vinyl cyclohexane and their hydrides; , Hydrides of aromatic ring moieties of polymers of vinyl aromatic monomers such as α-methylstyrene; and the like, and vinyl alicyclic hydrocarbon polymers and vinyl aromatic monomers, and these Any of random copolymers with other monomers copolymerizable with monomers, copolymers such as block copolymers, and hydrides thereof may be used. Examples of the block copolymer include diblock, triblock, or more multiblock and gradient block copolymers, and are not particularly limited.

  The molecular weight of the alicyclic structure-containing polymer used in the present invention is appropriately selected according to the purpose of use, but is a gel permeation chromatograph of a cyclohexane solution (a toluene solution when the polymer resin does not dissolve). The weight average molecular weight measured in terms of polystyrene is usually 5,000 or more, preferably 5,000 to 500,000, more preferably 8,000 to 200,000, and particularly preferably 10,000 to 100,000. When it is within the range, the mechanical strength and the moldability are highly balanced, which is preferable.

The glass transition temperature of the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300 ° C, preferably 100 to 280 ° C, and particularly preferably 115 to 250. When the temperature is in the range of 130 ° C., more preferably 130 to 200 ° C., the heat resistance and the moldability are highly balanced and suitable.
In the present invention, the glass transition temperature is measured based on JIS K7121.

  Incidentally, these alicyclic structure-containing polymers can be used alone or in combination of two or more.

<Soft polymer>
The soft polymer is a polymer having a Tg of usually 30 ° C. or lower, as described in JP-A-2006-124580, etc., and when there are a plurality of Tg, at least the lowest Tg is 30 ° C. or lower. It is a polymer. Among such soft polymers, those having a melt mass flow rate (MFR) of 10 g / 10 min to 100 g / 10 min at 230 ° C. and 2.16 kg measured according to JIS K 7210 are preferable.
The blending amount of such a soft polymer is 0.05 to 0.5 parts by weight, and more preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the alicyclic structure-containing polymer. If the amount of the soft polymer is too large, the transparency is lowered. On the other hand, if the amount is too small, white turbidity under high temperature and high humidity conditions cannot be suppressed.

Examples of such soft polymers include liquid polyethylene, polypropylene, poly-1-butene, ethylene / α-olefin copolymers, propylene / α-olefin copolymers, ethylene / propylene / diene copolymers (EPDM). ), Olefin-based soft polymers such as ethylene / propylene / styrene copolymers; isobutylene-based soft polymers such as polyisobutylene, isobutylene / isoprene rubber, isobutylene / styrene copolymers; polybutadiene, polyisoprene, butadiene / styrene random copolymers Polymer, isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene / butadiene / styrene / block copolymer , Diene-based soft polymers such as isoprene / styrene copolymer, styrene / isoprene / styrene block copolymer; silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, dihydroxypolysiloxane; polybutyl acrylate , Polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, soft polymers made of α, β-unsaturated acid such as butyl acrylate / styrene copolymer; polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, Soft polymers comprising unsaturated alcohols such as vinyl acetate / styrene copolymers and amines or acyl derivatives or acetals thereof; polyethylene oxide, polypropylene oxide, epichlorohydrin rubber, Any epoxy-based soft polymer; fluorine-based soft polymer such as vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber; natural rubber, polypeptide, protein, polyester-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, Examples thereof include soft polymers such as polyamide-based thermoplastic elastomers. These soft polymers may have a cross-linked structure or may have a functional group introduced by a modification reaction.
Among such soft polymers, diene-based soft polymers are preferable because they are particularly excellent in transparency and high-temperature and high-humidity resistance, and diene-based soft polymers using styrene are particularly preferable. Propylene) block-polystyrene is preferred from the viewpoint of high temperature and high humidity resistance.
Among these soft polymers, the difference (| nD (A) −nD (B) between the refractive index (nD (A)) of the alicyclic structure-containing polymer and the refractive index (nD (B)) of the soft polymer. It is preferable to select a material having a relationship of |) of less than 0.005 because an optically molded product having excellent transparency can be easily obtained.

  These soft polymers can be used alone or in combination of two or more.

<Terpene phenol resin>
A terpene phenol resin is, for example, a cationic polymerization reaction of 1 mol of a terpene compound and 0.1 to 15 mol of phenol under a Friedel-Craft catalyst at a temperature of −10 to 120 ° C. for 0.5 to 20 hours. Can be manufactured.

The terpene compound that is one of the raw materials for the terpene phenol resin will be described.
The terpene compound is generally a polymer of isoprene (C ₅ H ₈ ), and is classified into monoterpene (C ₁₀ H ₁₆ ), sesquiterpene (C ₁₅ H ₂₄ ), diterpene (C ₂₀ H ₃₂ ), and the like. A terpene compound is a compound having these as a basic skeleton. Of these, monoterpenes are preferably used in the present invention.
Specific examples of these terpene compounds include the following, but the present invention is not limited thereto.

  As the terpene compound, myrcene, alloocimene, ocimene, α-pinene, β-pinene, dipentene, limonene, α-ferrandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineol, 1,4-cineole, Examples include α-terpineol, β-terpineol, γ-terpineol, camphene, tricyclene, sabinene, paramentadienes, and carenes. Among these compounds, α-pinene, β-pinene, limonene, myrcene, alloocimene and α-terpinene are particularly preferably used in the present invention.

  Examples of phenols include, but are not limited to, phenol, cresol, xylenol, catechol, resorcin, hydroquinone, bisphenol A, and the like.

  Examples of Friedel-Craft catalysts include, but are not limited to, zinc chloride, titanium tetrachloride, tin chloride, aluminum chloride, boron trifluoride, iron chloride, antimony trichloride, and the like.

Commercially available terpene phenol resins include the Polystar series and Mighty Ace series manufactured by Yashara Chemical.
Hydrogenated terpene resin oligomers obtained by hydrogenating these terpene phenol resins can also be used.

The blending amount of the [B] terpene phenol resin with respect to 100 parts by weight of the [A] alicyclic structure-containing polymer blended in the present invention is 1 to 15 parts by weight, preferably 2 to 10 parts by weight, more preferably. Is 3 to 5 parts by weight. If the amount of the terpene phenol resin is too large, the thermal stability will be reduced, or mold stains will occur during molding. .

In the present invention, compounding agents other than those described above can be mixed and used in the alicyclic structure-containing polymer composition as necessary.
Other compounding agents are not particularly limited as long as they are usually used in thermoplastic resin materials. For example, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, mold release agents, Coloring agents such as dyes and pigments, compounding agents such as plasticizers, antistatic agents, and optical brighteners can be used.

The mixing method of the alicyclic structure-containing polymer, the soft polymer, the terpene phenol resin, and other compounding agents used as necessary is not particularly limited as long as the compounding agent is sufficiently dispersed in the polymer. . Moreover, there is no special restriction | limiting in the order of a mixing | blending. Examples of the compounding method include a method of kneading a resin in a molten state with a mixer, a single-screw kneader, a twin-screw kneader, a roll, a Brabender, an extruder, etc., a solidifying method by dissolving and dispersing in an appropriate solvent, Or a method of removing the solvent by a direct drying method.
When a biaxial kneader is used, after kneading, it is usually extruded in a rod shape in a molten state, cut into an appropriate length with a strand cutter, and pelletized in many cases.

<Optical molding>
The alicyclic structure-containing polymer composition of the present invention is a known thermoplastic resin molding method, for example, injection molding method, extrusion molding method, cast molding method, inflation molding method, blow molding method, vacuum molding method, press molding. It can be formed into a molded body by a molding method, a compression molding method, a rotational molding method, a calendar molding method, a rolling molding method, a cutting molding method or the like.
Among these, an injection molding method or a press molding method that is excellent in dimensional accuracy and can be molded into an aspherical shape is preferable, and an injection molding method is particularly preferable.
Specific examples of the optical molded body thus molded include an imaging lens for a camera, an imaging lens for a video camera, a microscope lens, an endoscope lens, a telescope lens, a binocular lens, a spectacle lens, and a magnifying lens. All-light transmission lens, optical disk pickup lens, laser beam printer fθ lens, sensor lens, laser scanning lens, camera finder prism lens, infrared sensor lens, autofocus lens, bandpass filter lens, etc. Optical lenses; optical disc substrates such as DVDs (digital video discs); optical mirrors; prisms; light guide plates such as liquid crystal displays; optical films such as polarizing films, retardation films, and light diffusion films.
Among these molded products, in particular, the polymer composition of the present invention is applied to a relatively thick optical molded product having a thickness of 0.1 mm or more, preferably 0.1 to 30 mm, more preferably 1 to 10 mm. Shows remarkable effect.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited only to these examples. In the following examples and comparative examples, “part” or “%” is based on weight unless otherwise specified.

In the following Examples and Comparative Examples, various physical properties are measured as follows.
(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. As standard polyisoprene, Tosoh Corporation standard polyisoprene, Mw = 602, 1,390, 3,920, 8,050, 13,800, 22,700, 58,800, 71,300, 109,000, 280 A total of 10 points of 1,000 were used.
For the measurement, Tosoh HLC8120GPC was used, and Tosoh TSKgel G5000HXL, TSKgel G4000HXL and TSKgel G2000HXL were connected in series as a column. Performed under conditions.
(2) The hydrogenation rate was measured by ¹ H-NMR using deuterated chloroform as a solvent.
(3) The glass transition temperature is based on JIS K 7121, using a differential scanning calorimeter (manufactured by Nanotechnology, product name “DSC6220S11”), heated to 30 ° C. or higher from the glass transition temperature, and then cooled at a rate of cooling − It measured in the process of cooling to room temperature at 10 degree-C / min, and heating up at a temperature increase rate of 10 degree-C / min after that.

(4) High temperature and high humidity resistance (micro crack)
A molded product having a thickness of 5 mm or 9 mm and a length and width of 65 mm is produced by injection molding, and the molded product is kept in an environment of 85 ° C. and 90% relative humidity for 1000 hours in a high-temperature and high-humidity tester, and rapidly The sample was taken out to the outside and allowed to stand at room temperature for 72 hours, and then white light was incident from the side, and the microcracks were visually observed.
The evaluation index is ○ when the micro-crack is not generated in the molded product, Δ when the micro-crack is generated in the range of less than 30% of the molded product, and micro-crack is generated in the range of 30% or more of the molded product The case where it did is made x.
(Haze)
Among the molded products produced by the microcrack evaluation, the haze was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name “NDH2000”). After the haze measurement, the molded product is kept in an environment of 85 ° C. and 90% relative humidity for 1000 hours in a high-temperature and high-humidity tester, and is rapidly taken out to room temperature (outside the tester) and placed in room temperature for 72 hours. The haze was measured, and the amount of increase in haze obtained by subtracting the haze before the high-temperature and high-humidity test from the haze after the high-temperature and high-humidity test was used as an index for high-temperature and high-humidity resistance. The smaller the increase in haze before and after the high-temperature and high-humidity test, the better the high-temperature and high-humidity resistance.
(5) Lowering of glass transition temperature (Tg) A molded product having a thickness of 5 mm and a length and width of 65 mm was produced by injection molding, and Tg was measured using a differential scanning calorimeter (product name “DSC6220S11”, manufactured by Nanotechnology). It was measured. The Tg of the injection molded product was subtracted from the Tg of the polymer before blending the terpene phenol resin, the soft polymer, and dipentaerythritol tetrastearate, and the amount of decrease in Tg was confirmed. It shows that thermal stability is so high that the fall amount of Tg is small.

[Polymer production example]
<Production Example 1>
To an autoclave equipped with a stirrer purged with nitrogen, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (1,4-methano-1,4,4a, 9a-tetrahydrofluorene was added. ) 400 parts, cyclohexane 600 parts, toluene 300 parts, 1-hexene 1.55 parts by weight. After the solution was heated to 45 ° C., 3.7 parts by weight of a 15% toluene solution of triisobutylaluminum as a ring-opening polymerization catalyst, 0.20 parts by weight of isobutyl alcohol, 0.86 parts by weight of diisopropyl ether, and tungsten hexachloride 56.3 parts by weight of a 0.65 wt% cyclohexane solution was added and reacted at 45 ° C. for 1 hour. Thereafter, 0.7 parts by weight of isopropyl alcohol was added to stop the reaction.
20 parts by weight of a nickel-silica supported catalyst (manufactured by JGC Catalysts & Chemicals, product name “E22U”) was added to the reaction solution, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and a temperature of 180 ° C. for 6 hours.
After completion of the reaction, this solution was filtered through a filter having a pore size of 2 μm to remove the hydrogenation catalyst. The filtrate was poured into 5000 parts by weight of stirred isopropyl alcohol to precipitate a hydrogenated product, which was collected by filtration.
The obtained hydrogenated product was dried at 100 ° C. for 24 hours at 1 mmHg or less to obtain 300 parts by weight of an alicyclic structure-containing polymer A. The weight average molecular weight (Mw) of the alicyclic structure-containing polymer A was 32,000, the molecular weight distribution (Mw / Mn) was 2.1, the Tg was 156 ° C., and the refractive index was 1.5350. Further, the hydrogenation rate of the main chain was 99% or more, and the hydrogenation rate of the aromatic ring was 99% or more.
<Production Example 2>
To a stainless steel pressure vessel substituted with nitrogen, 76.8 parts of styrene and 3.2 parts of isoprene were added and mixed and stirred to prepare a mixed monomer. Next, 320 parts of dehydrated cyclohexane, 4 parts of mixed monomer and 0.1 part of dibutyl ether were charged into a stainless steel autoclave equipped with a nitrogen-substituted electromagnetic stirrer and stirred at 50 ° C. with a hexane solution of n-butyllithium ( Polymerization was started by adding 0.454 parts (concentration 15%) and polymerization was performed. After 0.5 hours had elapsed from the start of polymerization (the polymerization conversion rate at this point was about 96%), 76 parts of the mixed monomer was continuously added over 1 hour. 0.5 hours after the end of the addition of the mixed monomer (the polymerization conversion rate at this time was about 95%), 0.1 part of isopropyl alcohol was added to stop the reaction, and random copolymerization of styrene-isoprene A polymerization reaction solution in which the coalescence was dissolved was obtained. Next, 3 parts of a nickel-silica supported catalyst (product name “E22U” manufactured by JGC Catalysts & Chemicals Co., Ltd.) is added to and mixed with 400 parts of the polymerization reaction solution to obtain a mixed liquid, which is equipped with an electric heating device and an electromagnetic stirring device. A stainless steel autoclave was charged. Hydrogen gas was supplied to the autoclave and a hydrogenation reaction was performed for 6 hours while maintaining the temperature inside the autoclave at 160 ° C. and 4.5 MPa while stirring.
Next, using a pressure filter (made by IHI, Funda filter) using Radiolite # 800 as a filter bed, pressure filtration was performed at a pressure of 0.25 MPa to obtain a colorless and transparent solution from which the catalyst was removed. . This hydrogenation reaction solution was poured into a mixed solution of 250 parts of acetone and 250 parts of isopropanol while stirring to precipitate a hydrogenated product, which was collected by filtration. The recovered hydrogenated product was further washed with 200 parts of acetone, and then dried for 24 hours in a vacuum dryer at 100 ° C., which was decompressed to 1 mmHg or less, to obtain an alicyclic structure-containing polymer B. The yield of the alicyclic structure-containing polymer B was 99%. The alicyclic structure-containing polymer B had a weight average molecular weight (Mw) of 91,000, a molecular weight distribution (Mw / Mn) of 1.27, a Tg of 126.5 ° C., and a refractive index of 1.5070.
<Example 1>
Using 100 parts by weight of the alicyclic structure-containing polymer A prepared in Production Example 1, 1.0 part of a terpene phenol resin (terpene phenol copolymer; product name “YS Polystar” manufactured by Yasuhara Chemical Co., Ltd.), soft polymer (polystyrene) -Poly (ethylene / propylene) block-polystyrene copolymer; manufactured by Kuraray Co., Ltd., product name "Septon (registered trademark) 8104", refractive index 1.5370, styrene content 60% by weight) 0.07 part and antioxidant Tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (manufactured by Ciba Specialty Chemicals; product name “Irganox (registered trademark) 1010”) Add 0.1 part each, twin screw kneader (Toshiba Machine Co., Ltd., product name "TEM-35B", screw diameter 37mm L / D = 32, screw rotation speed 150 rpm, resin temperature 250 ° C., feed rate 10 kg / hour) and extruded into a strand shape. This was cooled with water, cut with a pelletizer, and pelletized.

The obtained pellets were dried at 100 ° C. for 4 hours using a hot air dryer in which nitrogen was circulated, and then the cylinder temperature was 280 ° C. with an injection molding machine (manufactured by FANUC; ROBOSHOT (registered trademark) -2000i100A), gold Injection molding was performed under the conditions of a mold temperature of 145 ° C., an injection speed of 10 mm / second, a holding pressure of 700 kgf / cm ² , and a back pressure of 50 kgf / cm +, and a molded product having a length of 65 mm, a width of 65 mm, and a thickness of 5 mm, and a length of 65 mm A molded body of 65 mm and thickness 9 mm was obtained. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Example 2>
A molded body was obtained in the same manner as in Example 1 except that the amount of the terpene phenol resin was changed to 15 parts and the amount of the soft polymer was changed to 0.1 parts. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Example 3>
Using 100 parts by weight of the alicyclic structure-containing polymer B prepared in Production Example 2, the amount of the terpene phenol resin is 5 parts, and the soft polymer is polystyrene-poly (ethylene / propylene) block-polystyrene copolymer (Kuraray). Pellets were obtained in the same manner as in Example 1 except that the product name was changed to 0.2 parts manufactured by the company, product name “Septon (registered trademark) 2002”, refractive index 1.5035, styrene content 30% by weight.

The obtained pellets were dried at 100 ° C. for 4 hours using a hot air dryer in which nitrogen was circulated, and then the cylinder temperature was 250 ° C. with an injection molding machine (manufactured by FANUC; ROBOSHOT (registered trademark) -2000i100A) Injection molding was performed under the conditions of a mold temperature of 115 ° C., an injection speed of 10 mm / second, a holding pressure of 700 kgf / cm ² , and a back pressure of 50 kgf / cm ² , a molded body having a length of 65 mm, a width of 65 mm, and a thickness of 5 mm; A molded body having a width of 65 mm and a thickness of 9 mm was obtained. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Example 4>
A molded body was obtained in the same manner as in Example 1 except that the amount of the soft polymer was changed to 0.5 part. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Example 5>
A molded body was obtained in the same manner as in Example 1 except that the amount of the terpene phenol resin was changed to 2 parts and the amount of the soft polymer was changed to 0.3 parts. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Comparative Example 1>
A molded product was obtained in the same manner as in Example 3 except that 100 parts by weight of the alicyclic structure-containing polymer B prepared in Production Example 2 was used and dipentaerythritol tetrastearate was used instead of terpene phenol resin. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Comparative example 2>
A molded body was obtained in the same manner as in Example 1 except that the amount of the terpene phenol resin was changed to 20 parts and the amount of the soft polymer was changed to 0 parts. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Comparative Example 3>
A molded body was obtained in the same manner as in Example 1 except that the amount of the terpene phenol resin was changed to 0 part and the amount of the soft polymer was changed to 0.3 part. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Comparative example 4>
A molded body was obtained in the same manner as in Example 1 except that the amount of the soft polymer was changed to 1.0 part. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.
<Comparative Example 5>
A molded body was obtained in the same manner as in Example 2 except that the amount of terpene phenol resin was changed to 20 parts. Tg measurement and a high temperature and high humidity resistance test were performed using the obtained molded body. The results are shown in Table 1.

From this result, in addition to the soft polymer, what blended the terpene phenol resin with the alicyclic structure-containing polymer, only the soft polymer, than when only the terpene phenol resin was blended with the alicyclic structure-containing polymer, It turns out that it is excellent in high-temperature, high-humidity resistance (Examples 1, 2 and 5 and Comparative Examples 2 and 3).
It turns out that Tg of a molded object falls significantly when there is too much quantity of the terpene phenol resin to mix | blend (Example 2 and Comparative Example 5).
Moreover, when there is too much quantity of a soft polymer, it turns out that it is inferior to the transparency after a high temperature, high humidity test (Example 4 and Comparative Example 4).
Even if dipentaerythritol tetrastearate is blended in the same amount as the terpene phenol resin instead of blending the terpene phenol resin, it can be seen that the high-temperature and high-humidity resistance is insufficient and the Tg is significantly reduced (compared with Example 3). Example 1).

Claims (3)

[A] Fat containing 1 to 15 parts by weight of terpene phenol resin and 0.05 to 0.5 parts by weight of soft polymer for 100 parts by weight of alicyclic structure-containing polymer Ring structure-containing polymer composition.   An optical molded body comprising the alicyclic structure-containing polymer composition according to claim 1.   An optical lens having a thickness of 0.1 mm or more, comprising the alicyclic structure-containing polymer composition according to claim 1.