JP2011195623A - Thermoplastic resin composition for optical use and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for optical use which is excellent in resistance against blue-violet light or UV-light without deterioration of excellent molding processability, productivity, transparency, heat resistance and other characteristics due to thermoplasticity of a cyclic olefin-based ring opened polymer, and to provide molded products thereof.SOLUTION: The thermoplastic resin composition for optical use of the cyclic olefin-based ring opened polymer includes (A) 100 pts.wt. of the cyclic olefin-based ring opened polymer, (B) 0.1-3 pts.wt. of a phenolic oxidant, (C) 0.1-5 pts.wt. of a light-fastness stabilizer, (D) 0.01-1 pt.wt. of at least one light absorber for light with a specific wavelength, represented by a formula selected from formulas (1), (2), (3), and (4), which is a compound having an absorption rate in the entire wavelength region of ≥390 nm and ≤800 nm of ≤10%, and having a largest absorption wavelength in a range of wavelength of ≥200 nm and <390 nm, and having a heat loss at 200°C of ≤5 mass%, and (E) 0.1-9 pts.wt. of a phosphorous acid-based heat stabilizer.

Description

  The present invention relates to an optical thermoplastic resin composition of a cyclic olefin-based ring-opening copolymer having resistance to a specific light wavelength, and a molded article using the same.

    Resins composed of cyclic olefin-based ring-opening copolymers, and molded articles thereof have a low birefringence, excellent transparency to visible light, relatively high heat resistance, and low water absorption. For example, illumination members, optical sealing materials, optical storage media, protective films, retardation films, diffusion films mixed with light diffusing particles, and transparent conductive films having a conductive layer formed on the surface. It is used for applications such as an optical filter in which a coating layer such as vapor deposition for cutting a specific wavelength is formed, and a wavelength control element in which a specific shape is formed on the surface of the coating itself or on the coating layer on the surface.

In recent years, an optical semiconductor element used for a light source is being used with a short wavelength such as ultraviolet light excellent in energy efficiency and light control, or bluish purple light close to ultraviolet light.
However, as the wavelength of the light used becomes shorter, the amount of energy increases rapidly, and the resin that is an organic material has problems such as degradation of its molecular chain, degradation, discoloration, etc. due to short wavelength light. is there.

  Short wavelength light, which is high energy, causes the resin to melt and deform, as well as discoloration and thermal degradation, by converting the light energy of the absorbed short wavelength light into thermal energy, in addition to degradation due to resin molecular cleavage. There are problems that arise. Therefore, a material having short wavelength light resistance needs to have good transparency and short heat resistance to short wavelength light.

  As resins having relatively resistance to short wavelength light, there are fluorine resins such as polytetrafluoroethylene and polymethyl methacrylate. The former is due to the strong intermolecular bonding force, and it is difficult to break the molecular chain at a short wavelength of high energy, and the latter is due to good short wavelength transmission and less absorbed light. . However, the former is heat resistant and transparent, inferior to a cyclic olefin-based ring-opening copolymer, and expensive, and the latter is a curable resin and has a moldability compared to a thermoplastic cyclic olefin-based ring-opening copolymer. There are problems inferior in productivity and inferior heat resistance, and there are problems in that heat resistance and transparency, as well as moldability, productivity and price cannot be satisfied.

  In addition, transparent inorganic materials such as quartz glass with heat resistance, transparency, and resistance to short-wavelength light are produced due to inferior moldability and mass productivity compared to organic resins, and are brittle and inferior in impact resistance. There is a problem that it is easily damaged at the time of use.

  On the other hand, in order to prevent deterioration of the resin, a method of prescribing antioxidants and deterioration inhibitors such as phenols, phosphorus and sulfur, and short wavelength light such as ultraviolet rays in sunlight for resins used outdoors. A method of prescribing a light-resistant stabilizer or an ultraviolet absorber for preventing deterioration of the resin is a method that is conventionally used for general purposes. Since resin degradation due to short-wavelength light is caused by the molecular structure and molecular skeleton of the resin, even if a general-purpose antioxidant, light-resistant stabilizer, or ultraviolet absorber is generally prescribed, it will cause the resistance to deteriorate. Sometimes. In particular, lasers and optical semiconductors having high directivity and convergence are further required to have resistance to a specific wavelength, and thus there is no satisfactory organic material by the conventional method.

  A resin composition comprising a cyclic olefin-based ring-opening copolymer having excellent optical properties, heat resistance, and water absorption resistance, and a molded product thereof, a method of imparting resistance to short-wave light of high energy such as blue-violet light and ultraviolet light Is not known, and a resin composition comprising a cyclic olefin-based ring-opening copolymer excellent in short-wavelength light resistance and a molded product thereof have been demanded.

JP 7-48489 A JP 10-45981

"Principle of Polymer Degradation and its Application, 1st Edition" SCHNABLE, Junkichi Soma, Hanafusa Rin, 1993 "Degradation and stabilization of polymer materials" Zenjiro Osawa, Koji Kawamoto, Hideki Sakai, CMC, 1990 “Deterioration and stability of polymer compounds” Hideyuki Tsujioka Masahiro Tsunooka Toshiro Hayashi et al., IPC, 1987 "Durability Standard Test Method for Polymer Materials 2 Light and Ozone Resistance Test Method 1st Edition" Jun Hayakawa International Standards Study Group, IPC, 1992

  The present invention is an optical heat excellent in resistance to blue-violet light and ultraviolet light without impairing excellent properties such as molding processability, productivity, transparency and heat resistance due to thermoplasticity of the cyclic olefin ring-opening polymer. It is an object to provide a plastic resin composition and a molded product thereof.

The optical thermoplastic resin composition of the cyclic olefin ring-opening polymer of the present invention comprises 0.1 to 3 phenolic antioxidants (B) with respect to 100 parts by weight of the cyclic olefin ring-opening polymer (A). And at least one compound selected from the following formulas (1), (2), (3), and (4): 390 nm or more Light wavelength absorber (compound having a maximum absorption wavelength within a wavelength of 10% or less and less than 200 nm and less than 390 nm in an entire wavelength region of 800 nm or less, and having a loss on heating at 200 ° C. of 5% by mass or less. D) 0.01-1 part by weight;
An optical thermoplastic resin composition comprising 0.1 to 9 parts by weight of a phosphorous acid heat stabilizer (E).

［式（１）中のＲ¹〜Ｒ⁶は、水素原子、ハロゲン原子、炭素数１〜１５のアルキル基 、またはアルキル基の置換基を有してもよいアミノ基である。］

[R ^{1 to} R ⁶ in Formula (1) are a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or an amino group which may have a substituent of the alkyl group. ]

［式（２）中のＲ⁷は、炭素数１〜１５のアルキル基、または炭素数１〜１５のアルコキシル基である。Ｒ⁸、Ｒ⁹は、炭素数１〜１５のアルキル基である。］

[R ⁷ in the formula (2) is an alkoxy group of the alkyl group or 1 to 15 carbon atoms, 1 to 15 carbon atoms. R < ⁸ >, R < ⁹ > is a C1-C15 alkyl group. ]

［式（３）中のＲ¹⁰〜Ｒ¹³は、炭素数１〜１５のアルキル基である。］

[R < ¹⁰ > -R < ¹³ > in Formula (3) is a C1-C15 alkyl group. ]

［式（４）中のＲ¹⁴、Ｒ¹⁵は、炭素数１〜１５のアルキル基、またはアルコキシ基である。］
環状オレフィン系開環重合体（Ａ）としては、下記式（５）、式（６）、式（７）で表わされる構造単位を１種、あるいは複数を有する環状オレフィン系開環重合体の熱可塑性樹脂が好ましい。

[R < ¹⁴ >, R < ¹⁵ > in Formula (4) is a C1-C15 alkyl group or an alkoxy group. ]
As the cyclic olefin ring-opening polymer (A), the heat of the cyclic olefin ring-opening polymer having one or more structural units represented by the following formulas (5), (6), and (7): A plastic resin is preferred.

フェノール系酸化防止剤（Ｂ）は、下記式（８）で表され、且つ２００℃での加熱減量が１質量％以下の化合物が好ましい。

The phenolic antioxidant (B) is preferably a compound represented by the following formula (8) and having a heat loss at 200 ° C. of 1% by mass or less.

式（８）中のＲ³⁰は、ｎ価の脂肪族炭化水素基である。式（８）中のｎは、１〜４の整数である。

R ³⁰ in the formula (8) is an n-valent aliphatic hydrocarbon group. N in Formula (8) is an integer of 1-4.

  The light-resistant stabilizer (C) has at least one unit structure of tetramethylpiperidine represented by the following formula (9) and one unit structure of 1,3,5-triazine represented by the following formula (10). In addition, a light stabilizer having a molecular weight of 1000 or more and a heat loss at 200 ° C. of 1% by mass or less is preferable.

式（９）中のＭｅはメチル基であり、Ｒ³¹、Ｒ³²は、水素、もしくは、炭素、窒素、酸素、アルキレン基などの脂肪族炭化水素基、アミノ基、アミド基、イミノ基、アゾ基、カルボニル基などの連結基、もしくは式（９）の単位構造と式（１０）の単位構造が連結基を介さず、直接結合していても良い。

Me in the formula (9) is a methyl group, and R ³¹ and R ³² are hydrogen, aliphatic hydrocarbon groups such as carbon, nitrogen, oxygen, and alkylene groups, amino groups, amide groups, imino groups, azo groups. A linking group such as a group or a carbonyl group, or the unit structure of the formula (9) and the unit structure of the formula (10) may be directly bonded without a linking group.

  The light wavelength absorber (D) is at least one compound selected from the following formulas (1), (2), (3) and (4), and has an absorptance of 10% or less at a wavelength of 390 nm to 800 nm. In addition, a compound having a maximum absorption wavelength within a wavelength of 200 nm or more and less than 390 nm and a loss on heating at 200 ° C. of 5 mass% (hereinafter also referred to as “specific light wavelength absorber (D)”).

［式（１）中のＲ¹〜Ｒ⁶は、水素原子、ハロゲン原子、炭素数１〜１５のアルキル基 、またはアルキル基の置換基を有してもよいアミノ基である。］

[R ^{1 to} R ⁶ in Formula (1) are a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or an amino group which may have a substituent of the alkyl group. ]

［式（２）中のＲ⁷は、炭素数１〜１５のアルキル基、または炭素数１〜１５のアルコキシル基である。Ｒ⁸、Ｒ⁹は、炭素数１〜１５のアルキル基である。］

[R ⁷ in the formula (2) is an alkoxy group of the alkyl group or 1 to 15 carbon atoms, 1 to 15 carbon atoms. R < ⁸ >, R < ⁹ > is a C1-C15 alkyl group. ]

［式（３）中のＲ¹⁰〜Ｒ¹³は、炭素数１〜１５のアルキル基である。］

[R < ¹⁰ > -R < ¹³ > in Formula (3) is a C1-C15 alkyl group. ]

［式（４）中のＲ¹⁴、Ｒ¹⁵は、炭素数１〜１５のアルキル基、またはアルコキシ基である。］
亜燐酸系熱安定剤（Ｅ）は、下記式（１１）で示される亜燐酸エステルであり、分子量が６００以上で、２００℃での加熱減量が５質量％以下の化合物が好ましい。

[R < ¹⁴ >, R < ¹⁵ > in Formula (4) is a C1-C15 alkyl group or an alkoxy group. ]
The phosphorous acid heat stabilizer (E) is a phosphite ester represented by the following formula (11), preferably a compound having a molecular weight of 600 or more and a loss on heating at 200 ° C. of 5% by mass or less.

式（１１）中のＲ³³〜Ｒ³⁵ は、水素、水酸基、アリール基、アリル基、アルキル基、シクロアルキル基、ナフチル基、ビニル基、フェニル基、ベンジル基、ハロゲン基、アシル基、アセチル基、アルデヒド基、カルボキシル基、アジド−アジ基、アジ基、アミノ基、イソシアネート基、シアノ基、チオイソシアネート基、ニトロ基、ニトロソ基、硝酸エステル、ヒドロキシ基、スルホ基、イミノ基、ケトン基、チオキシ基などの極性基、メルカプト基、チオール基、アルキレン基、エステル結合、カルボニル基、ケテン、チオエステル、ウレタン結合、アゾ基、イソニトリル基、オキシム結合、ジイミド結合、エーテル結合、ジスルフィド結合、スルフィド結合、アミド結合、チオアミド結合、イミド結合、リン酸エステル、スルホニル結合、アレン、アミジン結合、チオ尿素などの連結基であり、これらの極性基や連結基を１種、或いは２種以上含んでもよく、複数の連結基が結合しても良い。また、式（１１）で示される構造単位が１個でも複数個含んでもよい。

R ^{33 to} R ³⁵ in the formula (11) are hydrogen, hydroxyl group, aryl group, allyl group, alkyl group, cycloalkyl group, naphthyl group, vinyl group, phenyl group, benzyl group, halogen group, acyl group, acetyl group Aldehyde group, carboxyl group, azido-azi group, azide group, amino group, isocyanate group, cyano group, thioisocyanate group, nitro group, nitroso group, nitrate ester, hydroxy group, sulfo group, imino group, ketone group, thioxy Polar groups such as groups, mercapto groups, thiol groups, alkylene groups, ester bonds, carbonyl groups, ketene, thioesters, urethane bonds, azo groups, isonitrile groups, oxime bonds, diimide bonds, ether bonds, disulfide bonds, sulfide bonds, amides Bond, thioamide bond, imide bond, phosphate ester, sulfonyl bond , An allene, an amidine bond, a thiourea, and the like, which may include one or more of these polar groups and linking groups, or a plurality of linking groups may be bonded. One or more structural units represented by the formula (11) may be included.

Hereinafter, the present invention will be specifically described.
<Cyclic olefin ring-opening polymer (A)>
Examples of the cyclic olefin ring-opening polymer used in the present invention include those described in Patent Documents 1 to 6.
[Patent Document 1] JP-A-1-132625 [Patent Document 2] JP-A-1-132626 [Patent Document 3] JP-A 63-218726 [Patent Document 4] JP-A-2-133413 Patent Document 5: Japanese Patent Application Laid-Open No. 61-120816 [Patent Document 6] Japanese Patent Application Laid-Open No. 61-115912 The cyclic olefin-based ring-opening polymer used in the present invention is a cyclic olefin-based monomer having a norbornene skeleton. It is a polymer obtained by homopolymerizing or copolymerizing the product, and examples thereof include the following.

(I) A ring-opening polymer of a cyclic olefin monomer.
(II) A ring-opening copolymer of a cyclic olefin monomer and a copolymerizable monomer.
(III) A hydrogenated (co) polymer of the ring-opening (co) polymer of (I) or (II) above.
(IV) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of (I) or (II) by Friedel-Craft reaction and then hydrogenating it.
(V) A saturated polymer of a cyclic olefin monomer and an unsaturated double bond-containing compound.
(VI) Addition type (co) polymers of cyclic olefin monomers and hydrogenated (co) polymers thereof.
(VII) An alternating copolymer of a cyclic olefin monomer and methacrylate or acrylate.

  As the cyclic olefin ring-opening polymer (hereinafter, also referred to as “cyclic olefin resin”) according to the present invention, the above (I), (II), and (III) are preferable, and the above (III) is more preferable. preferable.

  Preferred cyclic olefin-based resins according to the present invention include those having structural units represented by the following formula (5), formula (6), and formula (7). Such a cyclic olefin resin may be a resin containing only the structural unit represented by the formula (5), the structural unit represented by the formula (6), or the structural unit represented by the formula (7). Even a copolymer containing each structural unit of formula (6), formula (6), formula (7), formula (5), and formula (7), formula (5), formula (6), and formula (7) And a copolymer containing the respective structural units. Preferably, it is a resin of a copolymer containing only the structure of the formula (5) or the structural units of both the formula (5) and the formula (6).

式（５）、式（６）並びに、式（７）中のｍ、ｐ、ｑ、ｓ、ｔは、０以上の整数である。式（７）において、ｓ＝０且つｔ＝０は、除く。

M, p, q, s, and t in Formula (5), Formula (6), and Formula (7) are integers of 0 or more. In Expression (7), s = 0 and t = 0 are excluded.

X, Y, and Z in formula (5), formula (6), and formula (7) are each independently a group represented by the formula: —CH═CH— or a formula: —CH ₂ CH ₂ —. Is a group to be
R ^{16 to} R ²⁹ are represented by the following (i) to (vii), respectively.
(i) a hydrogen atom,
(ii) a halogen atom,
(iii) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms including a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
(Iv) a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms,
(V) a polar group,
(Vi) R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , or R ¹⁸ and R ¹⁹ in Formula 5, R ²⁰ and R ²¹ , R ²¹ and R ²² , R ²² and R ^{23 in} the structural unit of Formula 6 , R ²³ and R ²⁴ , or R ²⁴ and R ²⁵ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , or R ²⁸ and R ²⁹ in Formula 7, Represents an aromatic monocyclic or polycyclic carbocyclic ring or heterocyclic ring, and R ^{1 to} R ¹⁴ not involved in the bond are independently selected from the above (i) to (v);
(Vii) one or more of the (iv) hydrocarbon group or the (vi) carbocyclic or heterocyclic ring is the above (
It represents a halogen atom of ii) or a group substituted with a polar group of (v), or a group substituted with a halogen atom of (ii) and a polar group of (v).

Examples of the halogen atom (ii) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
(iii) The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms containing a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom is an alkyl such as a methyl group, an ethyl group or a propyl group. A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a propenyl group; The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. As the linking group, a divalent hydrocarbon group having 1 to 10 carbon atoms such as an alkylene group (—CH ₂ —), a vinyl group (—CH═CH—); a linkage containing oxygen, nitrogen, sulfur or silicon. Examples of the group include an ether bond (—O—), a diether bond (—O—O—), a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), and a sulfide bond (—S—). , Disulfide bond (—S—S—), sulfone group (—SO ₂ —), azo group (—N═N—), imino group (—NH—), amide bond (—NHCO—, —CONH—), Silyl group (—Si (R) ₂ — (wherein R is an alkyl group such as methyl or ethyl)), siloxane bond (—OSi (R) ₂ — (wherein R is an alkyl group such as methyl or ethyl) And a linking group containing a plurality of these may be used.

(iv) Substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups such as methyl, ethyl and propyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; vinyl groups and allyl groups. , An alkenyl group such as a propenyl group, and a phenyl group. The substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure, or may be bonded via a linking group. As the linking group, a divalent hydrocarbon group having 1 to 10 carbon atoms such as an alkylene group (—CH ₂ —), a vinyl group (—CH═CH—); a linkage containing oxygen, nitrogen, sulfur or silicon. Examples of the group include an ether bond (—O—), a diether bond (—O—O—), a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), and a sulfide bond (—S—). , Disulfide bond (—S—S—), sulfone group (—SO ₂ —), azo group (—N═N—), imino group (—NH—), amide bond (—NHCO—, —CONH—), Silyl group (—Si (R) ₂ — (wherein R is an alkyl group such as methyl or ethyl)), siloxane bond (—OSi (R) ₂ —, where R is an alkyl group such as methyl or ethyl )) And the like, and a linking group containing a plurality of these may be used.

Examples of the polar group (v) include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, a triorganosiloxy group, Examples thereof include an organosilyl group, an amino group, an acyl group, an alkoxysilyl group, a sulfonyl group, and a carboxyl group. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an aryl such as a benzoyloxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, Examples of the triorganosiloxy group include trimethylsiloxy group and triethylsiloxy group; examples of the triorganosilyl group include trimethyl Silyl groups, such as triethylsilyl group and the like; examples of the amino group include primary amino group, the alkoxysilyl group, for example a trimethoxysilyl group, a triethoxysilyl group.

In the structural unit represented by the formula (5), at least one of R ^{16 to} R ¹⁹ in the formula (5) has the polarity of (v) and does not have the polar group of (v) R ^{16 to} R ¹⁹ are preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. M in Formula (5) is an integer of 0-3, Preferably, it is an integer of 0-1. The polymer of the structural unit represented by Formula (5) with the same number of m in Formula (5) may be a copolymer of the structural unit represented by Formula (5) from which the number of m in Formula (5) differs. .

In the structural unit (6), R ^{20 to} R ²⁵ in the formula (6) are preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. P and q in the formula (6) are integers of 0 to 3, preferably p + q = 0 to 4, more preferably 0 to 2, particularly preferably p = 0 and q = 0. Even in the polymer of the structural unit represented by the formula (6) having the same number of p and q in the formula (65), the structural unit represented by the formula (6) having a different number of p and q in the formula (6) Copolymers of

In the structural unit (7), R ^{26 to} R ²⁹ in the formula (7) are preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms. S and t in Formula (7) are integers of 0 to 3, and s + t is an integer of 1 or more. Preferably, s + t = 1 to 4, more preferably 1 to 3, and particularly preferably s + t = 1. Even in the polymer of the structural unit represented by the formula (7) in which the number of s and t in the formula (7) is the same, the structural unit represented by the formula (7) in which the number of s and t in the formula (7) is different Copolymers of

  In the polymer cyclic olefin-based resin represented by the structural unit, the weight ratio of the structural unit represented by the formula (5) / the structural unit represented by the formula (6) / the structural unit represented by the formula (7) is preferably 100 to 50. / 0 to 30/0 to 20% by weight, more preferably 100 to 60/0 to 30/0 to 10% by weight, and particularly preferably 100 to 70/0 to 25/0 to 5% by weight.

≪Manufacture of cyclic olefin resin≫
The cyclic olefin resin according to the present invention has a repeating unit represented by the above formula (5), formula (6), or formula (7).

  The repeating units represented by the formula (5), formula (6), and formula (7) are represented by the following formula (5 ′), formula (6 ′), and formula (7 ′), respectively. It is derived from a cyclic olefin monomer by ring-opening (co) polymerization. These monomers are referred to as specific monomers.

前記式（５’）、式（６’）、式（７’）中のｍ、ｐ、ｑ、ｓ、ｔ、およびＲ¹⁶〜Ｒ²⁹は、それぞれ前記式（５）、式（６）、式（７）と同様である。

M, p, q, s, t, and R ^{16 to} R ²⁹ in the formula (5 ′), the formula (6 ′), and the formula (7 ′) are respectively the formula (5), the formula (6), It is the same as Expression (7).

As the cyclic olefin-based monomer represented by the formula (5 ′), formula (6 ′), or formula (7 ′), a compound having a norbornene skeleton can be used without particular limitation. Compounds can be used.
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-isopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-phenylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-heptadecylbicyclo [2.2.1] hept-2-ene,
5-heptylbicyclo [2.2.1] hept-2-ene,
5-pentadecylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5-pentylbicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonyl-5-methylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
6-ethylidene-2-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-cyano-8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-cyanotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [5.2.1.0 ^2,6 ] -8-decene,
Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Bicyclo [2.2.1] hept-2-ene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene and the like.

These may be used alone or in combination of two or more. Preferably, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, tricyclo [4.3.0.1 ^2,5 ] dec-3-ene, bicyclo [2.2.1] hept-2-ene, more preferably 8 -Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.

In the present invention, the repeating unit represented by the formula (5) preferably has a polar group, and the polar group is preferably a group represented by the following formula (12). That is, in the repeating unit represented by the formula (5) or the cyclic olefin monomer represented by the formula (5), at least one of R ^{16 to} R ¹⁹ is represented by the following formula (12). It is preferably a group.

前記式（１２）中のｕは０または、１以上の整数であり、Ｒ³⁶ は炭素原子１〜３０の炭化水素基である。前記式（１２）中のｕは、好ましくは、０または１〜５の整数であり、Ｒ³⁶ は炭素原子数１〜１５の炭化水素基であり、更に好ましくは、ｕは、０または１であり、Ｒ³⁶ は、炭素原子数１〜３のアルキル基である。

In the formula (12), u is 0 or an integer of 1 or more, and R ³⁶ is a hydrocarbon group having 1 to 30 carbon atoms. U in the formula (12) is preferably 0 or an integer of 1 to 5, R ³⁶ is a hydrocarbon group having 1 to 15 carbon atoms, and more preferably, u is 0 or 1. R ³⁶ is an alkyl group having 1 to 3 carbon atoms.

<Copolymerization with other polymerization monomers>
In addition to the cyclic olefin monomer represented by the above formula (5 ′), formula (6 ′), and formula (7 ′), other cyclic olefin monomers or copolymers may be used as long as the object of the present invention is not impaired. Other polymer monomers that can be polymerized can also be used as a copolymerization raw material. Examples of other polymer monomers include cycloolefin monomers such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclohexadiene, cyclooctadiene, styrene, methylstyrene, ethylene, chloroethylene, and fluoroethylene. Ring-opening copolymerization with conjugated and non-conjugated diene monomers such as vinyl acetate, vinyl chloride, butylene, isobrene, isoprene, butadiene, propylene, propadiene, hexadiene, heptadiene, pentadiene, diallyl disulfide, allylamine, acrylonitrile, acrylamide Thus, a copolymer can be formed.

<Copolymerization with polymer>
To the cyclic olefin monomer represented by the formula (5 ′), formula (6 ′) and formula (7 ′), an unsaturated polymer capable of copolymerization is added within a range not impairing the object of the present invention. A copolymer can be formed by copolymerization. Examples of the unsaturated polymer include unsaturated carbonization such as polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, acrylonitrile butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene. A copolymer can be formed by ring-opening copolymerization with a hydrogen-based polymer or the like.

<Molecular weight of polymer>
As the molecular weight of the cyclic olefin-based resin of the present invention, a polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is usually 3 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 ×. 10 ^{3 to} 3 × 10 ⁵ , more preferably 1 × 10 ⁴ to 2 × 10 ⁵ , and the weight average molecular weight (Mw) in terms of polystyrene is usually 5 × 10 ³ to 1 × 10 ⁶ , preferably 1. It is preferable that it is in the range of × 10 ^{4 to} 5 × 10 ⁵ , more preferably 2 × 10 ⁴ to 4 × 10 ⁵ .

  When the molecular weight is too small, the strength of the resulting film may be low, or the heat distortion resistance may be reduced. On the other hand, when the molecular weight is excessive, the solution viscosity and the melt viscosity become high, and the productivity and processability of the polymer of the present invention may be deteriorated. The molecular weight distribution (Mw / Mn) of the cyclic olefin-based resin according to the present invention is usually 1.5 to 10, preferably 2 to 8, more preferably 2 to 7.

<Glass transition temperature of polymer>
The glass transition temperature (Tg) of the cyclic olefin-based resin in the present invention is usually 70 to 300 ° C, preferably 90 to 250 ° C, more preferably 100 to 180 ° C. A Tg of 120 ° C. or higher is preferable because of having excellent heat resistance. When Tg is less than 70 ° C., the heat resistance is low, and there may be a problem that the optical property changes due to thermal deformation or heat. On the other hand, when Tg exceeds 300 ° C., the productivity and workability are inferior, and the cyclic olefin-based resin of the present invention may be thermally deteriorated or discolored due to a high processing temperature.

In this specification, the Tg of the cyclic olefin-based resin is the maximum peak of the differential differential scanning calorimetry curve obtained when measured with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 20 ° C./min. Plot the temperature (point A) and -20 ° C from the maximum peak temperature (point B) on the differential scanning calorimetry curve, and the tangent on the baseline starting from point B and the tangent starting from point A It is required as an intersection.
The cyclic olefin resin according to the present invention preferably has transparency and heat resistance, and preferably has a glass transition temperature of 120 ° C. or higher and a linear expansion coefficient of 7.0 × 10 ⁻⁵ / ° C. or lower.

<Polymerization catalyst>
As a catalyst used for the production of the cyclic olefin resin according to the present invention, for example,
A catalyst described in Olefin Metathesis and Metathesis Polymerization (KJIVIN, JCMOL, Academic Press 1997) is preferably used.

  Examples of such a catalyst include (a) at least one selected from compounds of W, Mo, Re, V and Ti, and (b) an alkali metal element such as Li, Na, K, Ru, Cs, Alkaline earth metal elements such as Mg, Ca, Sr and Ba, Group 12 elements such as Zn, Cd and Hg, Group 13 elements such as B, Al, Ga and In, Si, Ge, Sn and Pb Examples thereof include a metathesis catalyst composed of a combination of at least one selected from compounds having a group 14 element or the like and having at least one of the element-carbon bond or the element-hydrogen bond. In order to enhance the activity of the catalyst, the additive (c) described later may be added.

These can be used singly or in combination of two or more. Examples of the component (a) include compounds such as WCl ₆ , MoCl ₅ , and ReOCl ₃ . As the component (b), for example, n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl _2, methylalumoxane, and the like LiH. As the additive of component (c), for example, alcohols, aldehydes, ketones, amines and the like can be suitably used, and further, compounds described in JP-A-1-240517 can be used. it can.

  The amount of the metathesis catalyst used is the molar ratio of the component (a) and the sum of the monomers represented by the formula (5 ′), formula (6 ′) and formula (7 ′) (a) component: The monomer is usually 1: 500 to 1: 50000, preferably 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that the component (a): component (b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. As for the ratio of the component (a) to the component (c), the molar ratio (c) :( a) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1.

<Polymerization solvent>
Solvents for dissolving the monomer used in the ring-opening copolymerization reaction, the ring-opening polymerization catalyst, the molecular weight regulator and the like include alkanes such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cycloheptane, and the like. , Cycloalkanes such as cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, etc. Halogenated hydrocarbon compounds, saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate; dimethoxyethane, dibutyl ether, tetrahydrofuran What ethers there may be mentioned, and these can be used in combination either alone or in combination of two or more. Among these, the above aromatic hydrocarbons are preferable. As the amount of the solvent used, the weight ratio of the solvent: the monomer represented by the formula (5 ′), the formula (6 ′) and the formula (7 ′) is 1: 1 to 10: 1, preferably The amount is 1: 1 to 5: 1.

<Hydrogenation>
A polymer obtained by polymerizing the above cyclic olefin-based monomer can be used as the resin of the present invention as it is, but since it has an unsaturated bond in its molecule, heat, light, and oxygen It is preferable to reduce unsaturated bonds by hydrogenating unsaturated bonds in the polymer, because there is a possibility that discoloration or deterioration is likely to occur due to activity such as. A known method can be applied to the hydrogenation reaction. For example, the catalyst, solvent, temperature conditions, etc. described in JP-A-63-218726, JP-A-1-132626, JP-A-1-240517, JP-A-2-10221 and the like are applied. The cyclic olefin-based resin of the present invention can be obtained by carrying out the hydrogenation reaction.

As a method for the hydrogenation reaction, for example, a hydrogenation catalyst is added to a copolymer solution, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C., preferably 20 to 20 ° C. It is performed by operating at 180 ° C. As the hydrogenation catalyst, the aforementioned known catalysts can be used. For example, solid heterogeneous catalysts in which noble metals such as palladium, platinum, nickel, rhodium and ruthenium are supported on a carrier such as carbon, silica, alumina and titania, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum , Cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichloro A homogeneous catalyst such as carbonyltris (triphenylphosphine) ruthenium can be mentioned. The form of the catalyst may be powder or granular. These hydrogenation catalysts are used in such a ratio that the copolymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.

  The hydrogenation rate of the cyclic olefin resin is usually 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 99 mol% or more.

<Filtering>
It is preferable to remove foreign matters such as the above-mentioned specific polymer, copolymer, catalyst, and large particles, chemical gel, and undissolved substances in the additive with a filtration filter. Filtration can be carried out in each stage regardless of the raw material stage, the stage where it is dissolved in a solvent, the stage after polymerization, the stage after removal of the solvent, the stage where it is dissolved again in the solvent, and the stage immediately before molding. Preferably, it is preferably carried out at the stage after polymerization, the stage after removal of the solvent, and the stage immediately before molding, and the number of times of filtration may be one or more. As a filter used for filtration, a metal filter, a polymer filter, an inorganic filter, or the like used in a solvent, a polymer solution, a resin, or an elastomer can be used. The pore size of the filtration filter is preferably 0.01 to 600 μm, more preferably 0.1 to 300 μm.

<Phenolic antioxidant>
The phenol-based antioxidant (B) is represented by the following formula (8), and is also referred to as a compound having a weight loss on heating at 200 ° C. of 1% by mass or less (hereinafter referred to as “specific phenol-based antioxidant (B)”). ) Is preferred.

式（８）中のＲ³⁰は、ｎ価の脂肪族炭化水素基であり、好ましくは、炭素数が４以上の２価以上の脂肪族炭化水素基であり、更に好ましくは、炭素数４もしくは５の脂肪族炭化水素基である。式（８）中のｎは、１〜４の整数である。

R ³⁰ in formula (8) is an n-valent aliphatic hydrocarbon group, preferably a divalent or higher aliphatic hydrocarbon group having 4 or more carbon atoms, more preferably 4 or 5 aliphatic hydrocarbon groups. N in Formula (8) is an integer of 1-4.

  The purification purity is preferably 90% by mass, and more preferably 95% by mass or more. If the purity is low and there are many impurities, the optical loss increases, and the intended resistance cannot be obtained.

  Specific examples of the specific phenol-based antioxidant (B) include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (molecular weight: 1178, loss on heating: 0.1 % By mass or less), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (molecular weight: 531, loss on heating: 0.4% by mass), hexamethylenebis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) prochionate (molecular weight: 639, loss on heating: 0.1% by mass or less). Preferable is pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

<Light resistance stabilizer (C)>
The light-resistant stabilizer (C) has at least one unit structure of tetramethylpiperidine represented by the following formula (9) and one unit structure of 1,3,5-triazine represented by the following formula (10). A compound (hereinafter also referred to as “specific light stabilizer (C)”) is preferred.

式（９）中のＭｅはメチル基であり、Ｒ³¹、Ｒ³²は、水素、もしくは、炭素、窒素、酸素、アルキレン基などの脂肪族炭化水素基、アミノ基、アミド基、イミノ基、アゾ基、カルボニル基などの連結基、もしくは式（９）の単位構造と式（１０）の単位構造が連結基を介さず、直接結合していても良い。

Me in the formula (9) is a methyl group, and R ³¹ and R ³² are hydrogen, aliphatic hydrocarbon groups such as carbon, nitrogen, oxygen, and alkylene groups, amino groups, amide groups, imino groups, azo groups. A linking group such as a group or a carbonyl group, or the unit structure of the formula (9) and the unit structure of the formula (10) may be directly bonded without a linking group.

  The molecular weight is 1000 or more, preferably 1500 or more, and more preferably 2000 or more. When the molecular weight is less than 1000, problems such as separation and migration are likely to occur during mixing with the resin or molding.

  The loss on heating at 200 ° C. is 1% by mass or less, preferably 0.5% by mass or more, more preferably 0.1% by mass or more. When the loss on heating exceeds 1% by mass, problems such as separation and migration are likely to occur during mixing with the resin and molding.

As specific examples of the specific light stabilizer (C),
Poly [{6-[(1,1,3,3-tetramethylbutyl) amino} -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4 -Piperidyl) imino]] (molecular weight: 2000 to 3000, loss on heating: 0.7%), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine- 2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight: 2000-3100, loss on heating: 0.1% by mass or less), poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} { (2,2,6,6-tetramethyl-4-piperidyl) imino} penta Tylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}] (molecular weight: 2000 to 3500, loss on heating: 0.1% by mass or less), poly [{6- (1,1,3 , 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} octamethylene {(2,2, 6,6-tetramethyl-4-piperidyl) imino}] (molecular weight: 2000 to 3000, loss on heating: 0.1% by mass), poly [{6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} heptamethylene {(2,2,6,6-tetramethyl-4 -Piperidyl) imino}] (molecular weight: 2000-3) 00, loss on heating: 0.1% by mass or less), N, N ′, N ″, N ″ ′-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetramethyl) Piperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine / dimethyl succinate 1- (2-hydroxyethyl) -4-2,2,6,6- Tetramethylpiperidine = 90/10 (molecular weight: 2286, loss on heating: 0.7 mass%), dibutylamine · 1,3,5-triazine · N, N′-bis (1,2,6,6-tetramethyl -4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate (molecular weight: 2600-3400, loss on heating: 0.1% by mass) The following are preferable: Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl ) Imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}].

<Specific light wavelength absorber (D)>
The specific light wavelength absorber (D) is at least one compound selected from the following formulas (1), (2), (3), and (4), and has an absorptance of 10 to 390 nm to 800 nm. %, And a compound having a maximum absorption wavelength within a wavelength of 200 nm or more and less than 390 nm and a loss on heating at 200 ° C. of 5% by mass.

［式（１）中のＲ¹〜Ｒ⁶は、水素原子、ハロゲン原子、炭素数１〜１５のアルキル基 、またはアルキル基の置換基を有してもよいアミノ基である。］
炭素数１〜１５のアルキル基としては、メチル基、エチル基、プロピル基、イソプ ロピル基、ブチル基、ｔｅｒｔ−ブチル基などが挙げられ、メチル基、エチル基が好 ましい。アルキル基の置換基を有してもよいアミノ基としては、アミノ基、ジメチル アミノ基、ジエチルアミノ基、ジプロキルアミノ基、ジブチルアミノ基が挙げられ、 ジメチルアミノ基、ジエチルアミノ基が好ましい。

[R ^{1 to} R ⁶ in Formula (1) are a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or an amino group which may have a substituent of the alkyl group. ]
Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group, and a methyl group and an ethyl group are preferable. Examples of the amino group which may have a substituent of an alkyl group include an amino group, a dimethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group, and a dimethylamino group and a diethylamino group are preferable.

［式（２）中のＲ⁷は、炭素数１〜１５のアルキル基、または炭素数１〜１５のアルコキシル基である。Ｒ⁸、Ｒ⁹は、炭素数１〜１５のアルキル基である。］
炭素数１〜１５のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基などが挙げられ、メチル基、エチル基が好ましい。炭素数１〜１５のアルコキシル基としては、メトキシ基、エトキシ基が好ましい。

[R ⁷ in the formula (2) is an alkoxy group of the alkyl group or 1 to 15 carbon atoms, 1 to 15 carbon atoms. R < ⁸ >, R < ⁹ > is a C1-C15 alkyl group. ]
Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group, and a methyl group and an ethyl group are preferable. As a C1-C15 alkoxyl group, a methoxy group and an ethoxy group are preferable.

［式（３）中のＲ¹⁰〜Ｒ¹³は、炭素数１〜１５のアルキル基である。］
炭素数１〜１５のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基などが挙げられ、メチル基、エチル基が好ましい。

[R < ¹⁰ > -R < ¹³ > in Formula (3) is a C1-C15 alkyl group. ]
Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group, and a methyl group and an ethyl group are preferable.

［式（４）中のＲ¹⁴、Ｒ¹⁵は、炭素数１〜１５のアルキル基、またはアルコキシ基である。］
炭素数１〜１５のアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ−ブチル基、アルコキシ基としては、メトキシ基、エトキシ基、プロピルオキシ基、ブチルオキシ基などが挙げられ、メチル基、エチル基が好ましい。炭素数１〜１５のアルコキシル基としては、メトキシ基、エトキシ基が好ましい。

[R < ¹⁴ >, R < ¹⁵ > in Formula (4) is a C1-C15 alkyl group or an alkoxy group. ]
Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, and an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, and a butyloxy group. And a methyl group and an ethyl group are preferable. As a C1-C15 alkoxyl group, a methoxy group and an ethoxy group are preferable.

The wavelength absorptance of 390 nm to 800 nm of the specific light wavelength absorber (D) is 10% or less, preferably 6% or less, more preferably 5% or less.
The maximum absorption wavelength of the specific light wavelength absorber (D) is 200 nm or more and less than 390 nm, preferably 250 nm or more and less than 380 nm, more preferably 270 nm or more and less than 370.

The heat loss at 200 ° C. of the specific light wavelength absorber (D) is 5% by mass or less, preferably 3% by mass or less.
Specific examples of the specific light wavelength absorber (D) include dimethyl (p-methoxybenzylidene) malonate, tetra-ethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, the following formula (13), And a compound represented by the formula (14).

＜亜燐酸系熱安定剤（Ｅ）＞
亜燐酸系熱安定剤（Ｅ）は、下記式（１１）で示される亜燐酸エステルであり、分子量が６００以上で、２００℃での加熱減量が５質量％以下の化合物（以下、「特定亜燐酸系熱安定剤（Ｅ）」ともいう。）が好ましい。

<Phosphorous acid heat stabilizer (E)>
The phosphite-based heat stabilizer (E) is a phosphite ester represented by the following formula (11), a compound having a molecular weight of 600 or more and a weight loss on heating at 200 ° C. of 5% by mass or less (hereinafter referred to as “specific sulfite”). Phosphoric acid heat stabilizer (E) "is preferred.

式（１１）中のＲ³³〜Ｒ³⁵ は、水素、水酸基、アリール基、アリル基、アルキル基、シクロアルキル基、ナフチル基、ビニル基、フェニル基、ベンジル基、ハロゲン基、アシル基、アセチル基、アルデヒド基、カルボキシル基、アジド−アジ基、アジ基、アミノ基、イソシアネート基、シアノ基、チオイソシアネート基、ニトロ基、ニトロソ基、硝酸エステル、ヒドロキシ基、スルホ基、イミノ基、ケトン基、チオキシ基などの極性基、メルカプト基、チオール基、アルキレン基、エステル結合、カルボニル基、ケテン、チオエステル、ウレタン結合、アゾ基、イソニトリル基、オキシム結合、ジイミド結合、エーテル結合、ジスルフィド結合、スルフィド結合、アミド結合、チオアミド結合、イミド結合、リン酸エステル、スルホニル結合、アレン、アミジン結合、チオ尿素などの連結基であり、これらの極性基や連結基を１種、或いは２種以上含んでもよく、複数の連結基が結合しても良い。また、式（１１）で示される構造単位が１個でも複数個含んでもよい。

R ^{33 to} R ³⁵ in the formula (11) are hydrogen, hydroxyl group, aryl group, allyl group, alkyl group, cycloalkyl group, naphthyl group, vinyl group, phenyl group, benzyl group, halogen group, acyl group, acetyl group Aldehyde group, carboxyl group, azido-azi group, azide group, amino group, isocyanate group, cyano group, thioisocyanate group, nitro group, nitroso group, nitrate ester, hydroxy group, sulfo group, imino group, ketone group, thioxy Polar groups such as groups, mercapto groups, thiol groups, alkylene groups, ester bonds, carbonyl groups, ketene, thioesters, urethane bonds, azo groups, isonitrile groups, oxime bonds, diimide bonds, ether bonds, disulfide bonds, sulfide bonds, amides Bond, thioamide bond, imide bond, phosphate ester, sulfonyl bond , An allene, an amidine bond, a thiourea, and the like, which may include one or more of these polar groups and linking groups, or a plurality of linking groups may be bonded. One or more structural units represented by the formula (11) may be included.

The heat loss at 200 ° C. of the specific phosphorous acid heat stabilizer (E) is 5% by mass or less, preferably 3% by mass or less.
As a specific example of the specific phosphorous acid heat stabilizer (E),
Tris (2,4-di-tert-butylphenyl) phosphite (loss on heating: 0.4% by mass), Tris (2,5-di-tert-butylphenyl) phosphite (loss on heating: 0.4% by mass) ), 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)] phosphite ( Loss on heating: 0.1% by mass or less), distearyl pentaerythritol diphosphite (loss on heating: 0.1% by mass or less), triisodecyl phosphite (loss on heating: 1.4% by mass), bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (loss on heating: 0.1% by mass), bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphat (Loss on heating: 0.1% by mass), bis (2,5-di-tert-butylphenyl) pentaerythritol diphosphite (loss on heating: 0.1% by mass), 2,2′-methylenebis (4 6-di-tert-butylphenyl) octyl phosphite (loss on heating: 0.1% by mass), bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid (heating Weight loss: 0.1% by mass or less), 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane ( Loss on heating: 0.1% by mass or less), 1,1′-biphenyl-4,4′-diylbis [bis (2,4-di-tert-butylphenyl) phosphonite]] (loss on heating: 0.1% by mass) % Or less), 3, -Bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane (loss on heating: 0.1% by mass or less) It is done.

<Addition amount>
The addition amount of the phenolic antioxidant (B) is 0.1 parts by weight or more and 3 parts by weight or less, preferably 0.3 parts by weight or more with respect to 100 parts by weight of the cyclic olefin ring-opening polymer (A). 2 parts by weight or less, more preferably 0.5 parts by weight or more and 1 part by weight or less. If the amount is less than 0.1 part by weight, the light resistance cannot be obtained, and if it exceeds 3 parts by weight, there is a possibility of causing problems such as surface migration and light scattering due to internal aggregation.

  The light stabilizer (C) is added in an amount of 0.1 parts by weight or more and 5 parts by weight or less, more preferably 0.5 parts by weight or more and 1 part by weight per 100 parts by weight of the cyclic olefin ring-opening polymer (A). Less than parts by weight. If the amount is less than 0.1 part by weight, the light resistance cannot be obtained, and if it exceeds 3 parts by weight, there is a possibility of causing problems such as surface migration and light scattering due to internal aggregation.

  The addition amount of the light wavelength absorber (D) is 0.01 part by weight or more and 1 part by weight or less, preferably 0.03 part by weight or more and 0.5 part by weight or less, more preferably 0.05 part by weight or more and 0.0. 3 parts by weight or less. If it is less than 0.01 part by weight, light resistance cannot be obtained, and if it exceeds 1 part by weight, coloring due to surface migration or absorption in the visible light region may occur.

  The amount of the phosphorous acid heat stabilizer (E) added is 0.1 to 9 parts by weight, preferably 0.2 weights per 100 parts by weight of the cyclic olefin ring-opening copolymer (A). Part to 6 parts by weight, more preferably 0.6 part to 4 parts by weight.

  The phosphorous acid heat stabilizer (E) has an effect of suppressing discoloration of the phenolic antioxidant (B), and as a result, improves the light resistance of the optical thermoplastic resin composition. The structural unit represented by the formula (7) constituting the phenolic antioxidant (B) is 100 moles, and the structural unit represented by the formula (10) constituting the phosphorous acid thermal stabilizer (E) is 30. By adding at a ratio of not less than 70 mol and not more than 70 mol, preferably not less than 40 mol and not more than 60 mol, more preferably 50 mol, a more light-resistant effect is exhibited.

<Other additives>
The optical thermoplastic resin composition of the present invention has a weathering agent, anti-aging agent, thermal polymerization inhibitor, leveling agent, surfactant, storage stabilizer, plasticizer, lubricant, inorganic filler, as long as the properties are not impaired. Agents, organic fillers, surface treatment agents such as organic silane coupling agents and organic titanium coupling agents, wettability improvers, water repellents, oil repellents, antifouling agents, flame retardants, antibacterial agents, anti-condensation agents, Additives used for known resins and elastomers such as coating surface improvers, antistatic agents, organic or inorganic conductive agents, and heat dissipation agents can be added. In addition, as long as the properties of the optical thermoplastic resin composition of the present invention are not impaired, the optical design is carried out with a light scattering agent such as an ultraviolet scattering agent, a visible light scattering agent, an infrared scattering agent, or a light diffusion as necessary. Agents, benzimidazole, benzindole, benzotriazole, benzothiazole, benzoxazole, rhodanine, cyanine, merocyanine, rhodocyanine, styryl, base styryl, oxonol, and other infrared absorbers such as fine inorganic particles, ultraviolet absorbers, Pigments, dyes, sensitizing dyes, fluorescent brighteners and the like can be added.

<Mixing method>
A mixing method of the cyclic olefin ring-opening polymer (A), the phenolic antioxidant (B), the light stabilizer (C), the light wavelength absorber (D), and the phosphorous acid heat stabilizer (E) is: Known mixing methods used for general-purpose resins and elastomers can be used. For example, a heat mixing method using a single screw extruder, a twin screw extruder, a Banbury mixer, a planetary mixer, a kneader, a roll, a feeder ruder, an extruder, etc., or a solution mixing method of dissolving and stirring in an organic solvent may be used. I can do it. Moreover, it can also mix by adding and stirring to the polymer solution after the completion | finish of superposition | polymerization at the time of manufacture of a cyclic olefin type ring-opening copolymer (A).

  It is obtained by kneading each component. The kneading temperature when heating and mixing is preferably 100 to 350 ° C, more preferably 150 to 300 ° C. Moreover, when kneading each component, each component may be kneaded in a lump or may be added and kneaded in several times. The kneading may be carried out by a multistage addition method using an extruder, and in the case of solution mixing, the cyclic olefin ring-opening polymer (A), the phenolic antioxidant (B), and the light stabilizer (C ), A specific light wavelength absorber (D), and a phosphorous acid heat stabilizer (E) may be dissolved in an organic solvent such as a hydrocarbon organic solvent such as toluene, hexane, cyclohexane, methylene chloride, Halogenous organic solvents such as ethylene chloride and carbon tetrachloride, and ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone can be used. Moreover, you may use 1 type, or 2 or more types of mixing methods.

<Molding method>
As a molding method of the optical thermoplastic resin composition to be applied, known molding methods used for resins and elastomers can be used, for example, superheat press molding, uniaxial extrusion molding, biaxial extrusion molding, T-die extrusion molding. , Profile extrusion molding, multilayer extrusion molding, melt casting, calendar molding, roll molding, roll press molding, blow molding, inflation molding, spray up molding, powder slush molding, flash molding, injection molding, injection compression molding, vacuum injection molding And heat molding such as melt casting, solution injection molding, solution casting and the like.

<Secondary processing>
The molded product of the applied optical thermoplastic resin composition can use a known secondary processing used in resins and elastomers, for example, uniaxial stretching, biaxial stretching, cutting, punching, and pasting. Combine processing, ball processing, heat press processing, laminating processing, welding processing, magnetic processing, secondary press processing, stamp processing, drawing processing, bending processing, etc. can be used.

<Surface treatment of molded products>
The molded article of the present thermoplastic resin composition can be subjected to known surface treatments used for resins and elastomers, for example, corona treatment, low temperature plasma treatment, atmospheric pressure plasma treatment, glow discharge treatment, etc. Treatment, ittro treatment, flame treatment, ittro treatment, ultrasonic treatment, laser ablation treatment, sand blast treatment, chemical corrosion treatment, buff treatment, primer treatment, coating treatment, dyeing treatment, plating treatment, vapor deposition treatment, printing treatment, sputtering treatment, etc. Surface treatment can be performed.

  In addition, plating, physical vapor deposition, chemical vapor deposition, vacuum vapor deposition, reactive vapor deposition, sputter vapor deposition, CDV treatment, ion plating, corona treatment, plasma treatment, ozone treatment anti-glare treatment, anti-reflection, as long as the target characteristics are not impaired. Surface treatment such as treatment, corrosion treatment, sandblast treatment, hard coat treatment, dipping coat, spray coat, flow coat, shower coat, roll coat, spin coat, gravure coat, micro gravure coat, comma roll coat, Mayer bar coat , Slot-by coating, air knife coating, lip coating, kiss coating, brush coating, and the like can be performed.

<Example>
<Cyclic olefin ring-opening polymer (A)>
<Synthesis Example 1>
As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (monomer 1-a) 100 parts, molecular weight regulator 1-hexene 3.6 parts and toluene 200 parts were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. did. To this, 0.17 part of a 1.5 mol / l toluene solution of triethylaluminum ((C ₂ H ₅ ) ₃ Al) as a polymerization catalyst and tungsten hexachloride (WCl ₆ ) modified with t-butanol and methanol And 1.0 part of a WCl ₆ solution (concentration 0.05 mol / l) in which the molar ratio of t-butanol to methanol and tungsten was 0.35: 0.3: 1 was added, and 3 parts at 80 ° C. were added. A ring-opening polymerization reaction was carried out by heating and stirring for a time to obtain a polymer solution (A-1). The polymerization conversion rate in this polymerization reaction was 97%.

4000 parts of the obtained polymer solution (A-1) was put in an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to 0.48 parts of the polymer solution (A-1). In addition, the hydrogenation reaction was performed by heating and stirring for 3 hours under conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution, the hydrogen gas was released, and this reaction solution was poured into a large amount of methanol to separate and recover a solidified product. The recovered coagulated product was dried to obtain a hydrogenated polymer (A-1).

The hydrogenation rate of the thus obtained hydrogenated polymer (A-1) was measured using 400 MHz ¹ H-NMR and found to be 99.9%.
With respect to the obtained polymer, the intrinsic viscosity (ηinh) measured in chloroform at 30 ° C. was 0.85 dl / g.

  The glass transition temperature (Tg) of this hydrogenated polymer was measured by DSC method and found to be 168 ° C. Further, when the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by the GPC method (solvent: tetrahydrofuran), the number average molecular weight (Mn) was 54500, and the weight average molecular weight (Mw) was 158000, The molecular weight distribution (Mw / Mn) was 2.90.

<Synthesis Example 2>
As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (monomer 1-a), 225 parts, bicyclo [2.2.1] hept-2-ene (monomer 1-b), 25 parts, and molecular weight regulator 18 parts of 1-hexene and 750 parts of toluene were charged into a nitrogen-substituted reaction vessel and heated to 60 ° C. Modified to, triethylaluminum _{((C 2 H 5) 3} Al) solution in toluene 0.62 parts of 1.5 mol / l as a polymerization catalyst, tungsten hexachloride modified with t- butanol and methanol (WCl ₆₎ Then, 3.7 parts of a WCl ₆ solution (concentration 0.05 mol / l) in which the molar ratio of t-butanol to methanol and tungsten was 0.35: 0.3: 1 was added and heated at 80 ° C. for 3 hours. The ring-opening copolymerization reaction was carried out by stirring to obtain a ring-opening copolymer solution (A-2). The polymerization conversion rate in this polymerization reaction was 97%.

4000 parts of the obtained ring-opening copolymer solution was put in an autoclave, and 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the copolymer solution (A-1). A hydrogenation reaction was performed by heating and stirring for 3 hours under conditions of a hydrogen gas pressure of 10 MPa and a reaction temperature of 165 ° C.

  After cooling the obtained reaction solution, the hydrogen gas was released, and this reaction solution was poured into a large amount of methanol to separate and recover a solidified product. The recovered coagulated product was dried to obtain a hydrogenated polymer (A-2).

The hydrogenation rate of the hydrogenated copolymer (A-2) thus obtained was measured using 400 MHz ¹ H-NMR and found to be 99.9%.
Moreover, when the ratio of the structural unit resulting from bicyclo [2.2.1] hept-2-ene (monomer 1-b) was measured using 400 MHz ¹ H-NMR, it was 10.2%. .

About the obtained copolymer, the intrinsic viscosity ((eta) inh) measured in 30 degreeC chloroform was 0.67 dl / g.
The glass transition temperature (Tg) of this hydrogenated copolymer was measured by DSC method and found to be 130 ° C. Further, when the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene were measured by GPC method (solvent: tetrahydrofuran), the number average molecular weight (Mn) was 39000, and the weight average molecular weight (Mw) was 116000, The molecular weight distribution (Mw / Mn) was 2.97.

<Synthesis Example 3>
As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (monomer 1-a) 71 parts, bicyclo [2.2.1] hept-2-ene (monomer 1-b) 1 part, and tricyclo [4. 3.0.1 ^2,5 ] together with 15 parts by mass of deca-3-ene (monomer 2-a), 18 parts of hexene and 200 parts by mass of toluene as a molecular weight regulator, charged in a nitrogen-substituted reaction vessel, 100 Heated to ° C. To this, 0.005 part of triethylaluminum, 0.005 part of methanol-modified tungsten hexachloride having a mass ratio of methanol: phenylphosphonic dichloride (PhPOCl ₂ ): tungsten hexachloride (WCl ₆ ) = 103: 630: 427 The reaction was allowed to proceed for 1 minute, and then 10 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (monomer 2-a) and bicyclo [2.2.1] hept-2-ene ( An additional 3 parts of monomer 1-b) was added in 5 minutes and allowed to react for an additional 45 minutes. Next, the obtained copolymer solution was placed in an autoclave, and 200 parts of toluene was further added. Next, 1 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a reaction modifier and RuHCl (CO) [P (C ₆ H ₅ ) _{3 as a} hydrogenation catalyst are used. ] After adding 0.006 parts by mass of ₃ and heating to 155 ° C., hydrogen gas was charged into the reactor, and the hydrogen gas pressure was adjusted to 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 parts by mass of toluene, 3 parts by mass of distilled water, 0.72 parts by mass of lactic acid, and 0.00214 parts by mass of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes. Thereafter, 200 parts by mass of methanol was added and heated at 60 ° C. for 30 minutes, and when cooled to 25 ° C., it was separated into two layers. Remove 500 parts by mass of the supernatant, again add 350 parts by mass of toluene and 3 parts by mass of water and heat at 60 ° C. for 30 minutes, then add 240 parts by mass of methanol and heat at 60 ° C. for 30 minutes to cool to 25 ° C. Separated into two layers. Remove 500 parts by mass of the supernatant, further add 350 parts by mass of toluene and 3 parts by mass of water, heat at 60 ° C. for 30 minutes, then add 240 parts by mass of methanol and heat at 60 ° C. for 30 minutes to cool to 25 ° C. Separated into two layers. Finally, after removing 500 parts by mass of the supernatant, the remaining polymer solution was filtered using 2.0 μm, 1.0 μm, and 0.2 μm filters. Thereafter, the solid content of the polymer was concentrated to 55%, the solvent was removed at 250 ° C., 4 torr, and a residence time of 1 hour, and the polymer was passed through a 10 μm polymer filter to obtain a copolymer (A-3). The hydrogenation rate of the thus obtained hydrogenated copolymer (A-3) measured by 400 MHz ¹ H-NMR was 99.9%. The measured proportion of the structural unit resulting from the respective monomers by using 400MHz ¹ H-NMR, 8- methyl-8-carboxymethyl tetracyclo [4.4.0.1 ^2.5. 1 ^7.10] -3-dodecene (monomer 1-a) due to the polymer / bicyclo [2.2.1] hept-2-ene (monomer 1-b) due to the polymer / tricyclo [ 4.3.0.1 ^2,5 ] Deca-3,7-diene (monomer 2-a) -derived polymer = 69.77 / 4.23 / 26.01% by weight. Tg measured by DSC method is 131 ° C., Mn by polystyrene conversion measured by GPC method is 16000, Mw is 61000, Mw / Mn is 3.81, and intrinsic viscosity (ηinh) in chloroform at 30 ° C. is 0.52 dl / G.
The glass transition temperature, hydrogenation rate, weight average molecular weight, molecular weight distribution, and relative viscosity were evaluated by the following methods.

Glass transition temperature (Tg )
Using a DSC6200 manufactured by Seiko Instruments Inc., the temperature increase rate was measured at 20 ° C. per minute under a nitrogen stream. Tg is the tangent on the baseline starting from point B, with the differential peak scanning calorie maximum peak temperature (point A) and the temperature at −20 ° C. from the maximum peak temperature (point B) plotted on the differential scanning calorimetry curve. And the intersection of the tangent starting from point A.

The hydrogenation rate nuclear magnetic resonance spectrometer (NMR) used was AVANCE 500 manufactured by Bruker, and ¹ H-NMR was measured using d-chloroform as the measurement solvent. The hydrogenation rate was calculated after calculating the monomer composition from the integral value of 5.1 to 5.8 ppm of vinylene group, 3.7 ppm of methoxy group, and 0.6 to 2.8 ppm of aliphatic proton.

Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography (Tosoh Co., Ltd. HLC-8220GPC, column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSKgel GMH _XL , TSK gel G2000H _XL , sequentially connected, solvent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by mass, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard material: manufactured by Tosoh Corporation Using TSK standard polystyrene), the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured. The Mn is a number average molecular weight.

Using a logarithmic viscosity Ubbelohde viscometer, the cyclic olefin resin was measured at 30 ° C. in chloroform (sample concentration: 0.5 g / dL). The soluble polyimide was measured in N-methyl-2-pyrrolidone (sample concentration: 0.5 g / dL) at 30 ° C.

As specific phenolic antioxidant (B),
(B-1) ADEKSTAB AO60 manufactured by Adeka Co., Ltd .: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], molecular weight 1178, loss on heating at 200 ° C. 0.001 Less than mass%.
(B-2) IRGANOX1076 manufactured by Ciba Japan Co., Ltd .: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, molecular weight 531, loss on heating at 200 ° C. 0.4% by mass .

As a specific light stabilizer (C),
(C-1) CHIMASSORB 944LD manufactured by Ciba Japan Co., Ltd .: Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} { (2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], molecular weight 2000-3100 at 200 ° C. Loss on heating 0.001% by mass.
(C-2) Ciba Japan Co., Ltd. CHIMASSORB 119FL: N, N ′, N ″, N ″ ′-tetrakis (4,6-bis (butyl- (N-methyl-2,2,6,6-tetra) Methylpiperidin-4-yl) amino) triazin-2-yl) -4,7-diazadecane-1,10-diamine / dimethyl succinate 1- (2-hydroxyethyl) -4-2,2,6,6 -Tetramethylpiperidine = 90/10, molecular weight 2286, loss on heating at 200 ° C 0.7 mass%.

As the specific light wavelength absorber (D),
(D-1) Hostavin PR-25 manufactured by Clarian: Dimethyl (p-methoxybenzylidene) malonate, molecular weight 250.25, loss on heating at 200 ° C. 0.14% by mass, maximum absorption wavelength 310 nm, absorption rate at 400 nm 0. 5%.
(D-2) Clariant Hostavin B-CAP: Tetra-ethyl-2,2 ′-(1,4-phenylene-dimethylidene) -bismalonate, molecular weight: 428.44, loss on heating at 200 ° C. 1.6% by mass The maximum absorption wavelength is 320 nm and the absorption rate is 400% at 400 nm.
(D-3) Clariant-made Hostavin VSU: 2-ethyl-2′-ethoxy-oxaanilide, molecular weight 312.37, loss on heating at 0.1% by mass or less, maximum absorption wavelength 282 nm, absorption at 400 nm 0. 7%.

As a specific phosphorous acid heat stabilizer (E),
(E-1) IRGANOX 168 manufactured by Ciba Japan Co., Ltd .: Tris (2,4-di-t-butylphenyl) phosphite, molecular weight 647, loss on heating at 200 ° C. 0.4% by mass.
(E-2) IRGANOX 12: 2,2 ′, 2 ″ -nitrilo [triethyl-tris (3,3 ′, 5,5′-tetra-tert-butyl-1,1′-) manufactured by Ciba Japan Co., Ltd. Biphenyl-2,2′-diyl)] phosphite, molecular weight 1463, loss on heating at 200 ° C. of 0.1% by weight or less.
(E-3) ADEKSTAB 3010 manufactured by Adeka Co., Ltd .: triisodecyl phosphite, molecular weight 503, loss on heating at 200 ° C. of 1.4% by mass.

<Comparative example>
As a light wavelength absorber (D ′),
(D′-4) TBO manufactured by Sumitomo Seika Co., Ltd .: 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene, molecular weight 431, loss on heating at 200 ° C. 0.1% by mass Hereinafter, the absorption rate is 59% at the maximum absorption wavelength of 376 nm and 400 nm.

<Adjustment of evaluation sample>
Specific phenolic antioxidant (B), specific light-resistant stabilizer (C), specific light wavelength absorber (D), and specific phosphorous acid-based thermal stability for 2 g of cyclic olefin-based ring-opening copolymer (A) The agent was prepared at the compounding ratio shown in Table 1, dissolved in 80 g of methylene chloride, stirred for 3 hours, solution cast on a smooth base glass, dried at room temperature for 8 hours, and vacuum dried at 50 ° C. for 8 hours to obtain a film thickness. A sample for evaluation of 100 μm ± 5 μm was obtained. The amount of residual solvent in the samples was all 0.01% by mass or less.

<Evaluation method>
(1) The maximum absorption wavelength and the absorption maximum absorption wavelength were measured using a U-3010 spectrophotometer manufactured by Hitachi High-Technologies Corporation.
(2) Absorptivity Absorbance is measured using a U-3010 spectrophotometer manufactured by Hitachi High-Technologies Corporation, using a sample prepared by dissolving a raw material in toluene at a concentration of 1% by mass. The absorption reflection was calculated from the measured value.

(3) Heat loss The heat loss at 200 ° C. was performed using a thermogravimetric measuring device TG-DTA2000SR manufactured by Bruker AXS Co., Ltd. Measurement was performed from room temperature to 400 ° C. under the setting conditions of a flow rate = 100 ml / min and a heating rate = 10 ° C./min, and the heating reduction rate up to 200 ° C. with respect to the measurement sample before heating was read.

(4) Light resistance evaluation A semiconductor laser element NDHV310APC manufactured by Nichia Corporation is incorporated in a temperature stable type LD projector TC20 with temperature stability type manufactured by Neoarc Co., Ltd., and a wavelength of 405 ± 5 nm is 50 mW / mm ² per unit area. The rate of decrease was calculated from the initial amount of transmitted energy and the amount of transmitted energy after 1000 hours.
◯: The rate of decrease is less than 5% x: The rate of decrease is 5% or more The time to decrease by 5% means the time when the rate of decrease exceeds 5%.

(5) Total light transmittance JIS K7361-1: 1997 "Test method for total light transmittance of plastic-transparent material: Part 1 single beam method using HAZE-GARD Co., Ltd. manufactured by Toyo Seiki Seisakusho Co., Ltd. The measurement was performed in accordance with the above.

(6) Transmittance at 405 nm The transmittance at a wavelength of 405 nm was measured using HAZE-GARD (Toyo Seiki Seisakusho).

  <Evaluation results>

Claims (5)

For 100 parts by weight of the cyclic olefin ring-opening polymer (A),
0.1 to 3 parts by weight of a phenolic antioxidant (B),
0.1 to 5 parts by weight of a light-resistant stabilizer (C),
It is at least one compound selected from the following formulas (1), (2), (3), and (4), and has an absorptance of a wavelength of 390 nm to 800 nm of 10% or less and a wavelength of 200 nm to less than 390 nm There is a maximum absorption wavelength in the light wavelength absorber (D) 0.01 to 1 part by weight, which is a compound having a loss on heating at 200 ° C. of 5% by mass or less,
An optical thermoplastic resin composition comprising 0.1 to 9 parts by weight of a phosphorous acid heat stabilizer (E).

[R ^{1 to} R ⁶ in Formula (1) are a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, or an amino group which may have a substituent of the alkyl group. ]

[R ⁷ in the formula (2) is an alkoxy group of the alkyl group or 1 to 15 carbon atoms, 1 to 15 carbon atoms. R < ⁸ >, R < ⁹ > is a C1-C15 alkyl group. ]

[R < ¹⁰ > -R < ¹³ > in Formula (3) is a C1-C15 alkyl group. ]

[R < ¹⁴ >, R < ¹⁵ > in Formula (4) is a C1-C15 alkyl group or an alkoxy group. ] 2. The optical thermoplastic resin composition according to claim 1, wherein the phenolic antioxidant (B) is a compound represented by the following formula (8) and having a heat loss at 200 ° C. of 1% by mass or less.

[R ³⁰ in Formula (8) is an n-valent aliphatic hydrocarbon group. N in Formula (8) is an integer of 1-4. ] The light-resistant stabilizer (C) has at least one unit structure of tetramethylpiperidine represented by the following formula (9) and one unit structure of 1,3,5-triazine represented by the following formula (10). The optical thermoplastic resin composition according to claim 1 or 2, which is a compound having a molecular weight of 1000 or more and a weight loss on heating at 200 ° C of 1% by mass or less.

[Me in Formula (9) is a methyl group, R ³¹ and R ³² are hydrogen or an aliphatic hydrocarbon group such as carbon, nitrogen, oxygen, alkylene group, amino group, amide group, imino group, A linking group such as an azo group or a carbonyl group, or the unit structure of the formula (9) and the unit structure of the formula (10) may be directly bonded without a linking group. ] The phosphorous acid heat stabilizer (E) is a phosphite ester represented by the following formula (11), a compound having a molecular weight of 600 or more and a loss on heating at 200 ° C of 5% by mass or less. The thermoplastic resin composition for optics in any one of -3.

[R ³³ to R ³⁵ in the formula (11) is hydrogen, hydroxyl, aryl group, an allyl group, an alkyl group, a cycloalkyl group, a naphthyl group, a vinyl group, a phenyl group, a benzyl group, a halogen group, an acyl group, an acetyl Group, aldehyde group, carboxyl group, azido-azi group, azide group, amino group, isocyanate group, cyano group, thioisocyanate group, nitro group, nitroso group, nitrate ester, hydroxy group, sulfo group, imino group, ketone group, Polar group such as thioxy group, mercapto group, thiol group, alkylene group, ester bond, carbonyl group, ketene, thioester, urethane bond, azo group, isonitrile group, oxime bond, diimide bond, ether bond, disulfide bond, sulfide bond, Amide bond, thioamide bond, imide bond, phosphate ester, sulfonyl bond Linking groups such as allene, amidine bond, thiourea, etc., and these polar groups or linking groups may be contained alone or in combination of two or more, and a plurality of linking groups may be bonded. One or more structural units represented by the formula (11) may be included. ]   The molded article obtained from the thermoplastic resin composition for optics in any one of Claims 1-4.