JP5601056B2 - Resin composition and optical component comprising the same - Google Patents

Description

The present invention relates to a resin composition comprising a cyclic olefin resin and a specific antioxidant.
More specifically, the present invention relates to a resin composition capable of molding an optical component without causing gas generation and dust generation even under severe processing conditions, and without causing the molded product to be colored or gel in the molded product.

  Cyclic olefin-based resins have high glass transition temperature and high light transmittance, and low refractive index anisotropy, so they have features such as low birefringence compared to conventional optical films, heat resistance, It attracts attention as a thermoplastic resin excellent in transparency and optical properties.

  Therefore, by utilizing the above features, for example, in the fields of optical and optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates and low dielectric materials, and sealing materials such as optical semiconductor sealing, cyclic olefin-based resins are used. Application is under consideration.

  On the other hand, in order to meet the recent demands for reducing the weight, size and thickness of various members, processing under high temperature and high shear is required. However, the cyclic olefin-based resin needs to be subjected to severe conditions for processing because of its excellent heat resistance, and addition of an antioxidant is essential to suppress oxidative degradation. Patent Documents 1 and 2 disclose resin compositions containing cyclic olefin-based resins and various antioxidants, but the antioxidants used cannot withstand the processing temperatures of injection molding and extrusion molding, and 1 2) Decomposition and volatilization contaminates the mold or roll 2) Decomposition product causes side reaction to produce fine gel, which becomes a defect of optical component 3) Resin processed product turns yellow and appearance There was a problem such as damage.

  Therefore, development of a resin composition that solves the above problems and does not impair the high transparency, low coloring, and high heat resistance inherent to the cyclic olefin resin even when injection molding or extrusion molding is performed at a high temperature has been strongly desired. .

Japanese Patent No. 2977274 JP 2002-179875 A

  The present invention provides a resin composition that generates little gas and generates dust even when processed under high temperature and high shear, and does not impair the high transparency, low coloration, and high heat resistance inherent in cyclic olefin resins. Let it be an issue.

  The present inventors have found that a resin composition that solves the above problems can be obtained by containing a specific hindered phenol compound in a cyclic olefin resin, and completed the present invention.

That is, the present invention includes the following matters.
[1] A cyclic olefin resin (A) having a structural unit derived from a compound represented by the following formula (1), and a phenol type having two or more groups represented by the following formula (2) in one molecule A resin composition comprising a compound (B).

（式（１）中、aおよびｂはそれぞれ独立に０または１を表し、ｃおよびｄはそれぞれ独立に０〜２の整数を表す。Ｒ⁴〜Ｒ¹³は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を有する基で連結されていてもよい炭素原子数１〜３０の炭化水素基；またはその他の極性基を表す。Ｒ¹⁰とＲ¹¹、またはＲ¹²とＲ¹³とは一体化して２価の炭化水素基を形成してもよく、Ｒ¹⁰またはＲ¹¹と、Ｒ¹²またはＲ¹³とは相互に結合して単環もしくは多環の炭素環または複素環を形成してもよい。）

(In the formula (1), a and b each independently represent 0 or 1, c and d each independently represent an integer of 0 to 2. R ^{4 to} R ¹³ each independently represents a hydrogen atom; a halogen atom. A hydrocarbon group having 1 to 30 carbon atoms which may be linked by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, or other polar group, R ¹⁰ and R ¹¹ , or R ¹² And R ¹³ may be combined to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ are bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring. A ring may be formed.)

（式（２）中、Ｒ^14aおよびＲ^14bはそれぞれ独立に水素原子または直鎖状もしくは分岐状の炭素原子数１〜１０の炭化水素基、Ｒ¹⁵およびＲ¹⁶はそれぞれ独立に炭素原子数１〜１０の炭化水素基、Ｘはメチレン基または炭素原子数２〜１０のアルキレン基を表す。）

(In the formula (2), R ^14a and R ^14b are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently 1 carbon atom. -10 hydrocarbon group, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms.)

[2] The resin composition according to [1], wherein the phenolic compound (B) satisfies the following requirements (Bi) and (B-ii).
(B-i): molecular weight is 800 or more (B-ii): weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less

  [3] The resin composition as described in [1] or [2], wherein the phenol compound (B) is a compound represented by the following formula (2-1).

（式（２−１）中、Ｒ^14aおよびＲ^14bはそれぞれ独立に水素原子または直鎖状もしくは分岐状の炭素原子数１〜１０の炭化水素基、Ｒ¹⁵およびＲ¹⁶はそれぞれ独立に炭素原子数１〜１０の炭化水素基、Ｘはメチレン基または炭素原子数２〜１０のアルキレン基を表す。Ｙはｎ価の基であり、炭素原子数３〜１２の鎖状炭化水素基または炭素原子数４〜８の環状炭化水素基を表し、ｎは１〜４の整数である。）

(In formula (2-1), R ^14a and R ^14b are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently a carbon atom. A hydrocarbon group having 1 to 10 carbon atoms, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms, Y is an n-valent group, a chain hydrocarbon group having 3 to 12 carbon atoms or a carbon atom Represents a cyclic hydrocarbon group of formula 4-8, n is an integer of 1-4.)

  [4] The resin composition according to any one of [1] to [3], wherein the phenol compound (B) is a compound represented by the following formula (2-a).

〔５〕前記環状オレフィン系樹脂（Ａ）が開環（共）重合水添体（Ａ−２）であることを特徴とする〔１〕〜〔４〕のいずれかに記載の樹脂組成物。

[5] The resin composition according to any one of [1] to [4], wherein the cyclic olefin-based resin (A) is a ring-opening (co) polymerized hydrogenated product (A-2).

[6] A phosphorus-containing compound (C) that further satisfies the following requirements (Ci) and (C-ii) is further contained, and the phosphorus-containing compound (C) is based on 100 parts by weight of the cyclic olefin-based resin (A). 0.005 to 5 parts by weight of the resin composition according to any one of [1] to [5].
(Ci): In a single compound, the relative molecular mass is 400 or more, and in a polydisperse mixture, the weight average molecular weight (Mw) by gel permeation chromatography (GPC) is 400 or more,
(C-ii): Weight reduction rate when heated at 250 ° C. for 1 hour under nitrogen is 50% or less

  [7] The resin composition as described in [6], wherein the phosphorus-containing compound (C) includes a structure represented by the following formula (3).

（式（３）中、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立に炭素原子数１〜２０の炭化水素基を表し、Ａｒは芳香族基を表し、ｍ+ｎ＝０〜３の整数を表す。）

(In formula (3), R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, Ar represents an aromatic group, and m + n = 0 to an integer of 3). )

  [8] The phosphorus-containing compound (C) contains at least one selected from compounds represented by the following formulas (3-a) to (3-c) as a main component [6] or [6] 7].

〔９〕前記開環（共）重合水添体（Ａ−２）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）による重量平均分子量（Ｍｗ）が３０，０００〜２００，０００であることを特徴とする〔５〕に記載の樹脂組成物。

[9] The weight average molecular weight (Mw) of the ring-opening (co) polymerized hydrogenated product (A-2) by gel permeation chromatography (GPC) is 30,000 to 200,000 [ 5].

[10] The resin composition as described in [5] or [9], wherein the ring-opening (co) polymerized hydrogenated product (A-2) has a glass transition temperature (Tg) of 100 to 250 ° C. .
[11] The hydrogenation rate of the carbon-carbon double bond portion excluding the unsaturated bond of the aromatic ring of the ring-opening (co) polymerized hydrogenated product (A-2) is 90% or more [ [5], [9] or [10].

  [12] An optical component comprising the resin composition according to any one of [1] to [11].

  According to the present invention, by including a specific phenol compound in the cyclic olefin resin, there is little gas generation and dust generation due to decomposition or volatilization even if processed under high temperature or high shear, and the cyclic olefin resin is inherently A resin composition which does not impair the high transparency, heat resistance and low colorability possessed is obtained.

  Further, when a specific phosphorus-containing compound is used in combination with the phenolic compound, a hue improving effect is recognized even if the content of the phenolic compound is reduced, so that the quality balance can be controlled by required characteristics.

  Therefore, the resin composition of the present invention is suitable for an optical film, an optical disk, an optical lens, an optical fiber, a transparent plastic substrate, a low dielectric material and other electronic / optical materials, and an optical semiconductor sealing material.

Hereinafter, the resin composition of the present invention and the optical component comprising the resin composition will be described.
The resin composition of the present invention comprises a cyclic olefin resin (A) having a structural unit derived from a compound represented by the following formula (1), and two groups represented by the following formula (2) in one molecule. It contains the phenol compound (B) having the above.

式（１）中、aおよびｂはそれぞれ独立に０または１を表し、ｃおよびｄはそれぞれ独立に０〜２の整数を表す。Ｒ⁴〜Ｒ¹³は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を有する基で連結されていてもよい炭素原子数１〜３０の炭化水素基；またはその他の極性基を表す。Ｒ¹⁰とＲ¹¹、またはＲ¹²とＲ¹³とは一体化して２価の炭化水素基を形成してもよく、Ｒ¹⁰またはＲ¹¹と、Ｒ¹²またはＲ¹³とは相互に結合して単環もしくは多環の炭素環または複素環を形成してもよい。

In formula (1), a and b each independently represent 0 or 1, and c and d each independently represent an integer of 0 to 2. R ^{4 to} R ¹³ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 30 carbon atoms which may be linked by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or others Represents a polar group. R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ may be integrated to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ are bonded to each other to form a simple group. A ring or polycyclic carbocyclic or heterocyclic ring may be formed.

式（２）中、Ｒ^14aおよびＲ^14bはそれぞれ独立に水素原子または直鎖状もしくは分岐状の炭素原子数１〜１０の炭化水素基、Ｒ¹⁵およびＲ¹⁶はそれぞれ独立に炭素原子数１〜１０の炭化水素基、Ｘはメチレン基または炭素原子数２〜１０のアルキレン基を表す。

In the formula (2), R ^14a and R ^14b are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently a group having 1 to 1 carbon atoms. 10 hydrocarbon groups, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms.

[Cyclic olefin resin (A)]
The cyclic olefin resin (A) used in the present invention is at least one of the following polymers A-1 to A-6 derived from a compound represented by the following formula (1).
A-1: Ring-opening (co) polymer A-2 of the compound represented by the formula (1); Ring-opening (co) polymerization obtained by hydrogenating the ring-opening (co) polymer (A-1) Hydrogenated A-3; ring-opened (co) polymer (A-1) cyclized by Friedel-Craft reaction and then hydrogenated ring-opened (co) polymerized hydrogenated A-4; formula (1) Addition (co) polymer A-5 of a compound represented by formula: Addition copolymer A-6 of a compound represented by formula (1) and ethylene or monosubstituted ethylene; represented by formula (1) Addition copolymer of compound and at least one monomer selected from vinyl cyclic hydrocarbon and cyclic diene, and addition copolymer hydrogenated compound The compound represented by the following formula (1) will be described.

式（１）中、aおよびｂはそれぞれ独立に０または１を表し、ｃおよびｄはそれぞれ独立に０〜２の整数を表す。Ｒ⁴〜Ｒ¹³は、それぞれ独立に水素原子；ハロゲン原子；酸素原子、硫黄原子、窒素原子もしくはケイ素原子を有する基で連結されていてもよい炭素原子数１〜３０の炭化水素基；またはその他の極性基を表す。このうち、Ｒ⁴〜Ｒ⁹は好ましくは水素原子または炭素原子数１〜１０の炭化水素基を表し、より好ましくは水素原子または炭素原子数１〜４の炭化水素基を表し、特に好ましくは水素原子を表す。Ｒ⁴〜Ｒ⁹が上記の基であると、式（１）で表される化合物を収率良く製造することができる。Ｒ¹⁰〜Ｒ¹³はそのいずれかが水素原子であり、好ましくはＲ¹⁰とＲ¹¹、またはＲ¹²とＲ¹³とは一体化して２価の炭化水素基を形成するか、Ｒ¹⁰またはＲ¹¹と、Ｒ¹²またはＲ¹³とは相互に結合して単環もしくは多環の炭素環または複素環を形成する。Ｒ¹⁰〜Ｒ¹³が上記の構造であると、式（１）で表される化合物の製造が容易でそれから得られる環状オレフィン系樹脂（Ａ）はガラス転移温度（Ｔｇ）が高く、かつ、機械的強度に優れる。

In formula (1), a and b each independently represent 0 or 1, and c and d each independently represent an integer of 0 to 2. R ^{4 to} R ¹³ are each independently a hydrogen atom; a halogen atom; a hydrocarbon group having 1 to 30 carbon atoms which may be linked by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or others Represents a polar group. Among these, R ^{4 to} R ⁹ preferably represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably hydrogen. Represents an atom. When R ^{4 to} R ⁹ are the above groups, the compound represented by the formula (1) can be produced with high yield. Any of R ^{10 to} R ¹³ is a hydrogen atom, and preferably R ¹⁰ and R ¹¹ , or R ¹² and R ¹³ are combined to form a divalent hydrocarbon group, or R ¹⁰ or R ^11. And R ¹² or R ¹³ are bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring. When R ^{10 to} R ¹³ have the above structure, the compound represented by the formula (1) can be easily produced, and the cyclic olefin resin (A) obtained therefrom has a high glass transition temperature (Tg), Excellent mechanical strength.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group. Group and the like.

The hydrocarbon group having 1 to 30 carbon atoms may be directly bonded to the ring structure, or may be bonded to the ring through a linking group. Examples of the linking group include a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group); a group having an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom (for example, a carbonyl group (—CO— ), Oxycarbonyl group (—O (CO) —), carbonyloxy group (—COO—), sulfone group (—SO ₂ —), ether bond (—O—), thioether bond (—S—), imino group (-NH-), amide bond (-NHCO-, -CONH-) and siloxane bond (-OSi (R)-) (wherein R is an alkyl group such as a methyl group and an ethyl group) and the like are included. It may be a linking group.

  The other polar group is a polar group other than the hydrocarbon group bonded through the above linking group. For example, a hydroxyl group, an alkoxy group, a carbonyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, Examples thereof include an amide group, an imide group, a triorganosiloxy group, a triorganosilyl 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 arylcarbonyloxy group such as a benzoyloxy group; Examples of the carbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, and a biphenylyloxycarbonyl group; Trimethylsiloxy group, triethylsiloxy group, etc .; triorganosilyl group, trimethylsilyl group, triethylsilyl group, etc .; amino group, primary amine Amino group; the alkoxysilyl group, such as trimethoxysilyl group and triethoxysilyl group.

  In the compound represented by the above formula (1), a and b are each independently 0 or 1, and preferably a = b = 0. c and d are each independently an integer of 0 to 2, preferably an integer of 0 to 1, more preferably c = 0 and d = 0 or 1. When a to d are within this range, it is preferable in terms of the availability and economics of raw materials for producing the compound represented by formula (1) and the productivity of the compound represented by formula (1).

Specific examples of the compound represented by the formula (1) include
Bicyclo [2.2.1] hept-2-ene,

トリシクロ［４.３.０.１^2,5］−３−デセン、

Tricyclo [4.3.0.1 ^2,5 ] -3-decene,

トリシクロ[４．３．０．１^2,5]−デカ−３，８−ジエン

Tricyclo [4.3.0.1 ^2,5 ] -deca-3,8-diene

トリシクロ［４.４.０.１^2,5］−３−ウンデセン、

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,

テトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

ペンタシクロ［６.５.１.１^3,6.０^2,7.０^9,13］−４−ペンタデセン

Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene

ペンタシクロ［７.４.０.１^2,5.１^9,12.０^8,13］−３−ペンタデセン

Pentacyclo ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene

５−メチルビシクロ［２.２.１］ヘプト−２−エン、５−エチルビシクロ［２.２.１］ヘプト−２−エン、５−メトキシカルボニルビシクロ［２.２.１］ヘプト−２−エン、５−メチル−５−メトキシカルボニルビシクロ［２.２.１］ヘプト−２−エン、５−エチリデンビシクロ［２.２.１］ヘプト−２−エン、５−シアノビシクロ［２.２.１］ヘプト−２−エン、８−エチリデンテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン、８−エトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−ｎ−プロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−イソプロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−ｎ−ブトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−フェノキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−（1−ナフトキシ）カルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−（２−ナフトキシ）カルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−（４−フェニルフェノキシカルボニル）テトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−エトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−ｎ−プロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−イソプロポキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−ｎ−ブトキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−フェノキシカルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−（1−ナフトキシ）カルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−（２−ナフトキシ）カルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メチル−８−〈４−フェニルフェノキシ〉カルボニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、
ペンタシクロ［８.４.０.１^2,5.１^9,12.０^8,13］−３−ヘキサデセン

5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-ethylidenebicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2. 1] hept-2-ene, 8-ethylidene tetracyclo [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-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, 8-ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene, 8-n-propoxycarbonyl tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-n - butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-phenoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] 3-dodecene, 8- (1-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8- (2-naphthoxy) carbonyl tetracyclo [4. 4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8- (4-phenyl-phenoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodec Emissions, 8-methyl-8-ethoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl -8-n-propoxycarbonyl tetracyclo [4.4 .0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene , 8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8-phenoxycarbonyl tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-methyl-8- (1-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 - dodecene, 8-methyl-8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8 <4 off Enirufenokishi> carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,
Pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene

ヘプタシクロ［８．７．０．１^3,6．１^10,17．１^12,15．０^2,7．０^11,16］−４−エイコセン

Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-Eicosen

ヘプタシクロ［８.８.０.１^4,7.１^11,18.１^13,16.０^3,8.０^12,17］−５−ヘンイコセン、５−フェニルビシクロ［２.２.１］ヘプト−２−エン、５−フェニル−５―メチルビシクロ［２.２.１］ヘプト−２−エン、８−フェニルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、５−ｎ−ブチルビシクロ［２.２.１］ヘプト−２−エン、５−ｎ−ヘキシルビシクロ［２.２.１］ヘプト−２−エン、５−（２−シクロヘキセニル）ビシクロ［２.２.１］ヘプト−２−エン、５−ｎ−オクチルビシクロ［２.２.１］ヘプト−２−エン、５−ｎ−デシルビシクロ［２.２.１］ヘプト−２−エン、５−イソプロピルビシクロ［２.２.１］ヘプト−２−エン、５−（１−ナフチル）ビシクロ［２.２.１］ヘプト−２−エン、５−（２−ナフチル）ビシクロ［２.２.１］ヘプト−２−エン、５−（２−ナフチル）−５−メチルビシクロ［２.２.１］ヘプト−２−エン、５−（４−ビフェニル）ビシクロ［２.２.１］ヘプト−２−エン、５−（４−ビフェニル）−５−メチルビシクロ［２.２.１］ヘプト−２−エン、５−アミノメチルビシクロ［２.２.１］ヘプト−２−エン、５−トリメトキシシリルビシクロ［２.２.１］ヘプト−２−エン、５−トリエトキシシリルビシクロ［２.２.１］ヘプト−２−エン、５−トリｎ−プロポキシシリルビシクロ［２.２.１］ヘプト−２−エン、５−トリｎ−ブトキシシリルビシクロ［２.２.１］ヘプト−２−エン、５−クロロメチルビシクロ［２.２.１］ヘプト−２−エン、５−ヒドロキシメチルビシクロ［２.２.１］ヘプト−２−エン、５−シクロヘキセニルビシクロ［２.２.１］ヘプト−２−エン、５−フルオロビシクロ［２.２.１］ヘプト−２−エン、５−フルオロメチルビシクロ［２.２.１］ヘプト−２−エン、５−トリフルオロメチルビシクロ［２.２.１］ヘプト−２−エン、５,５−ジフルオロビシクロ［２.２.１］ヘプト−２−エン、５,６−ジフルオロビシクロ［２.２.１］ヘプト−２−エン、５,５−ビス（トリフルオロメチル）ビシクロ［２.２.１］ヘプト−２−エン、５,６−ビス（トリフルオロメチル）ビシクロ［２.２.１］ヘプト−２−エン、５−メチル−５−トリフルオロメチルビシクロ［２.２.１］ヘプト−２−エン、５,５,６−トリフルオロビシクロ［２.２.１］ヘプト−２−エン、５,５,６,６−テトラフルオロビシクロ［２.２.１］ヘプト−２−エン、８−フルオロテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−フルオロメチルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−トリフルオロメチルテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８,８−ジフルオロテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、１，４−メタノ−１，４，４ａ，９ａ−テトラヒドロフルオレン

Heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12,17] -5- henicosenoic, 5-phenyl-bicyclo [2.2.1] hept 2-ene, 5-phenyl-5-methylbicyclo [2.2.1] hept-2-ene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 -Dodecene, 5-n-butylbicyclo [2.2.1] hept-2-ene, 5-n-hexylbicyclo [2.2.1] hept-2-ene, 5- (2-cyclohexenyl) bicyclo [2.2.1] Hept-2-ene, 5-n-octylbicyclo [2.2.1] hept-2-ene, 5-n-decylbicyclo [2.2.1] hept-2-ene , 5-isopropylbicyclo [2.2.1] hept-2-ene, 5- (1-naphthyl) bicyclo [2.2.1] hept-2-ene, 5- (2-naphthyl) bicyclo 2.2.1] Hept-2-ene, 5- (2-naphthyl) -5-methylbicyclo [2.2.1] hept-2-ene, 5- (4-biphenyl) bicyclo [2.2. 1] hept-2-ene, 5- (4-biphenyl) -5-methylbicyclo [2.2.1] hept-2-ene, 5-aminomethylbicyclo [2.2.1] hept-2-ene 5-trimethoxysilylbicyclo [2.2.1] hept-2-ene, 5-triethoxysilylbicyclo [2.2.1] hept-2-ene, 5-trin-propoxysilylbicyclo [2. 2.1] hept-2-ene, 5-tri-n-butoxysilylbicyclo [2.2.1] hept-2-ene, 5-chloromethylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxymethylbicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicycle [2.2.1] hept-2-ene, 5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [2.2.1] hept-2-ene, 5- Trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.2.1] hept-2-ene, 5,6-difluorobicyclo [2.2.1] hept -2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2 -Ene, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene, 8-fluorotetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-fluoromethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-trifluoromethyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8,8-difluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3 -Dodecene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene

および［フルオレン−９,８'−トリシクロ［４.３.０.１^2,5］[３]デセン］などが挙げられ、このうち特に好ましくはビシクロ［２.２.１］ヘプト−２−エン、トリシクロ［４.３.０.１^2,5］−３−デセン、トリシクロ[４．３．０．１^2,5]−デカ−３，８−ジエン、テトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、１，４−メタノ−１，４，４ａ，９ａ−テトラヒドロフルオレン、５−メチル−５−メトキシカルボニルビシクロ［２.２.１］ヘプト−２−エン、５−エチリデンビシクロ［２.２.１］ヘプト−２−エン、８−エチリデンテトラシクロ［４.４.０.１^2,5.１^7,10］−３−ドデセン、８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセンおよび５−フェニルビシクロ［２.２.１］ヘプト−２−エンが挙げられる。
上記式(１)で表される化合物は、単独でまたは２種以上組み合わせて用いられる。

And [fluorene-9,8′-tricyclo [4.3.0.1 ^2,5 ] [3] decene], among which bicyclo [2.2.1] hept-2-ene is particularly preferable. , Tricyclo [4.3.0.1 ^2,5 ] -3-decene, tricyclo [4.3.0.1 ^2,5 ] -deca-3,8-diene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-dodecene, 1,4-methano -1,4,4a, 9a- tetrahydrofluorene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept -2 - ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methoxy Carbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and 5-phenylbicyclo [2.2.1] hept-2-ene.
The compounds represented by the above formula (1) are used alone or in combination of two or more.

(Copolymerizable monomer)
Examples of the copolymerizable monomer used to synthesize the above (A-1) to (A-6) include known cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.

  In the present invention, the cyclic olefin-based resin can be obtained by a known method, for example, by the methods described in JP-A Nos. 1-132626, 2006-77257, and 2008-955. What is obtained can be used.

  Of these cyclic olefin-based resins (A-1) to (A-6), (A-2) to (A-5) are preferable, and (A-2) is particularly preferable. The ring-opening (co) polymerized hydrogenated product (A-2) is preferable because it is excellent in heat resistance, mechanical strength, processability, transparency and productivity.

  The intrinsic viscosity [η] inh of the cyclic olefin resin (A) is preferably 0.2 to 5 dL / g, more preferably 0.3 to 3 dL / g, and particularly preferably 0.3 to 1.0 dL / g. is there.

  The weight average molecular weight (Mw) by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably 30,000 to 200,000, more preferably 32,000 using tetrahydrofuran of the cyclic olefin resin (A) as a solvent. ˜180,000, particularly preferably 35,000 to 160,000, and the molecular weight distribution (Mw / Mn) is preferably 1.5 to 4.0, more preferably 1.7 to 3.7. Yes, particularly preferably 2.0 to 3.5. In addition, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) of the ring-opening (co) polymerized hydrogenated product (A-2) which is a preferred embodiment of the cyclic olefin resin (A) is preferable. Is 30,000 to 200,000, more preferably 31,000 to 150,000, and particularly preferably 32,000 to 120,000. It is preferable that the weight average molecular weight (Mw) of the ring-opening (co) polymerized hydrogenated product (A-2) is in the above range since both workability and strength can be achieved.

  When the intrinsic viscosity [η] inh, weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) are in the above ranges, the cyclic olefin resin (A) has heat resistance, water resistance, chemical resistance and mechanical properties. It is good.

  As glass transition temperature (Tg) of the said cyclic olefin resin (A), it is 110-350 degreeC normally, Preferably it is 110-250 degreeC, More preferably, it is 110-220 degreeC, Most preferably, it is 110-200 degreeC. When Tg is less than 110 ° C., it may be deformed during use under high temperature conditions. On the other hand, when Tg exceeds 350 ° C., molding may be difficult. That is, when Tg exceeds 350 ° C., the heating temperature during the molding process must be increased, and the possibility that the resin is deteriorated by heat may increase. The glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated product (A-2) which is a preferred embodiment of the cyclic olefin resin (A) is preferably 100 to 250 ° C, more preferably 105 to 220 ° C. Especially preferably, it is 110-210 degreeC. It is preferable that the glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated product (A-2) is in the above range because melt processing is easy and there is practical heat resistance.

  When hydrogenating the said cyclic olefin resin (A), it is preferable that the hydrogenation rate of the carbon-carbon double bond except the unsaturated bond of an aromatic ring is 90% or more, and it is more preferable that it is 95% or more. preferable. When the hydrogenation rate is in the above range, heat resistance and colorability become better. If necessary, the unsaturated bond of the aromatic ring may be hydrogenated.

  Examples of the cyclic olefin resin (A) include specific hydrocarbon resins and specific known thermoplastic resins described in JP-A-9-221577 and JP-A-10-287732 as necessary. Further, thermoplastic elastomers, rubbery polymers, organic fine particles, inorganic fine particles and the like may be blended in an amount of 0 to 60% by weight.

[Phenolic compound (B)]
The phenolic compound (B) used in the present invention has two or more groups represented by the following formula (2) in one molecule.

式（２）中、Ｒ^14aおよびＲ^14bはそれぞれ独立に水素原子または直鎖状もしくは分岐状の炭素原子数１〜１０の炭化水素基を表し、Ｒ¹⁵およびＲ¹⁶はそれぞれ独立に炭素原子数１〜１０の炭化水素基を表す。上記炭素原子数１〜１０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基およびt−ブチル基などのアルキル基が挙げられる。このうち、Ｒ¹⁵としてはｔ−ブチル基が好ましく、Ｒ¹⁶としてはメチル基が好ましい。

In the formula (2), R ^14a and R ^14b each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ each independently represent the number of carbon atoms. 1 to 10 hydrocarbon groups are represented. Examples of the hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, and t-butyl group. Of these, t-butyl group is preferable as R ¹⁵ , and a methyl group is preferable as R ¹⁶ .

  X represents a methylene group or an alkylene group having 2 to 10 carbon atoms. Examples of the alkylene group having 2 to 10 carbon atoms include alkylene groups such as ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, s-butylene group and t-butylene group, Preferably an ethylene group is mentioned.

  The phenolic compound (B) preferably does not have an aliphatic ester structure. This is because the aliphatic ester structure has insufficient thermal stability, and therefore decomposes during high-temperature processing, and the resulting alcohol or carboxylic acid may react with the resin composition to form a microgel. The aliphatic ester structure is represented by —CO—O—R, where R is a linear or branched alkyl group.

  The phenolic compound (B) is preferably a compound represented by the following formula (2-1).

式（２−１）中、Ｘ、Ｒ^14a、Ｒ^14b、Ｒ¹⁵およびＲ¹⁶は上記式（２）と同義であり、Ｙはｎ価の基であり、炭素原子数３〜１２の鎖状炭化水素基または炭素原子数４〜８の環状炭化水素基を表し、ｎは１〜４の整数である。

In the formula (2-1), X, R ^14a , R ^14b , R ¹⁵ and R ¹⁶ have the same meaning as in the above formula (2), Y is an n-valent group, and is a chain having 3 to 12 carbon atoms. A hydrocarbon group or a C4-C8 cyclic hydrocarbon group is represented, and n is an integer of 1-4.

  Examples of the chain hydrocarbon group having 3 to 12 carbon atoms include propane, butane, pentane, hexane, heptane, and octane, and n hydrogens of these groups are represented by the formula (2). Has been replaced by Moreover, as said chain | strand-shaped hydrocarbon group, you may have a substituent other than group represented by Formula (2).

  Examples of the cyclic hydrocarbon group having 4 to 8 carbon atoms include cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and n hydrogens of these groups are represented by the formula (2). Has been replaced by Moreover, as said chain | strand-shaped hydrocarbon group, you may have a substituent other than group represented by Formula (2).

  Specific examples of the phenol compound (B) include 1,1,3-tris [2-methyl-4- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane.

フェノール系化合物は通常、酸化防止剤として知られ、分子量に対してフェノール構造部分が少ないと、本来の目的である酸化防止効果、すなわち、ラジカル補足能力が小さくなることが知られている。

Phenol compounds are generally known as antioxidants, and it is known that when the phenol structure portion is small relative to the molecular weight, the original antioxidant effect, that is, radical scavenging ability is reduced.

The phenolic compound (B) used in the present invention has a hindered structure in addition to having two or more phenolic structural parts such as the group represented by the formula (2) in one molecule, so that it is antioxidant. The side reaction of the agent is suppressed.
It is preferable to satisfy the requirements (B-i) and (B-ii) of the phenol compound (B).

(Bi): The molecular weight is 800 or more. The phenolic compound (B) may be a single compound or a mixture of compounds having various molecular weights (hereinafter referred to as “polydispersed mixture”). In the case of a single compound, the relative molecular mass is preferably 800 or more, more preferably 800 to 3000, particularly preferably 850 to 2800, and particularly preferably 900 to 2500. On the other hand, in the polydisperse mixture, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 800 or more, more preferably 800 to 4000, particularly preferably 850 to 3500, particularly preferably. Is 900 to 3000, and the molecular weight distribution (Mw / Mn) is 1.01 to 3.0, preferably 1.02 to 2.7, more preferably 1.03 to 2.5. When the molecular weight and molecular weight distribution of the phenolic compound (B) are in the above ranges, volatilization of the phenolic compound (B) during the processing of the resin composition is sufficiently suppressed, and an antioxidant is also present in the resin molded product. Oxidation degradation is suppressed over a long period because it has sufficient migration. In the present invention, only a single compound may be used as the phenol compound (B), or a polydisperse mixture may be used. The relative molecular mass refers to the mass of a molecule when the mass of carbon is 12.

(B-ii): The weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less, more preferably 13% or less, and particularly preferably 10% or less. When the weight reduction rate is in the above range, mold contamination and roll contamination due to pyrolyzate can be suppressed. The method of obtaining the weight reduction rate will be described. Using TG / DTA, the sample was heated from room temperature to 300 ± 5 ° C. at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere, held for 1 hour, Measure. The weight reduction rate (%) is determined from the initial weight and the weight after heating.

  The amount of the phenolic compound (B) added is usually 0.01 to 3 parts by weight, preferably 0.02 to 2.5 parts by weight, more preferably 100 parts by weight of the cyclic olefin resin (A). 0.03 to 2 parts by weight. When the addition amount of the phenolic compound (B) is in the above range, the oxidative deterioration of the resin composition of the present invention can be sufficiently prevented. Moreover, although the said phenolic compound (B) is comparatively low volatility, if it adds exceeding the said range, it exists in the tendency for the quantity of a volatile component to increase. In addition, the antioxidant may prevent the resin from being oxidized at a high temperature, but may deteriorate and color itself, and addition exceeding the necessary amount capable of preventing the oxidation of the resin may have an adverse effect. For this reason, it is desirable that the addition amount of the phenolic compound (B) is in the above range.

[Phosphorus-containing compound (C)]
The resin composition of the present invention may contain a phosphorus-containing compound (C) in addition to the cyclic olefin resin (A) and the phenolic compound (B). The phosphorus-containing compound (C) used in the present invention is not so high in its own thermal stability, but can improve the hue and processing stability of the resin composition. Here, the processing stability refers to, for example, minimizing gel generation, smoke generation, dust generation and the like when processing a resin composition. In addition, a phosphorus containing compound is normally known as antioxidant including the said phosphorus containing compound (C).
The structure of the phosphorus-containing compound (C) is not particularly limited as long as it satisfies the following (Ci) and (C-ii).

(Ci): When the molecular weight of the phosphorus-containing compound (C) is a single compound, the relative molecular mass thereof is preferably 400 or more, more preferably 400 to 3000, still more preferably 500 to 2700, particularly Preferably it is 600-2500. In the case of a polydisperse mixture, the weight average molecular weight (Mw) in terms of standard polystyrene by gel permeation chromatography (GPC) is preferably 400 or more, more preferably 400 to 5000, particularly preferably 450 to 4500, The molecular weight distribution (Mw / Mn) is 1.01 to 3.0, preferably 1.02 to 2.5, and more preferably 1.03 to 2.3. In the present invention, as the phosphorus-containing compound (C), only a single compound may be used, or a polydisperse mixture may be used. When the molecular weight and molecular weight distribution of the phosphorus-containing compound (C) are in the above ranges, the hue of the resin composition can be kept good, gel formation can be prevented, and smoke and dust can be minimized.

(C-ii): The weight loss rate when the phosphorus-containing compound (C) is heated at 250 ° C. for 1 hour under nitrogen is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less. is there. The method for obtaining the weight reduction rate will be described. Using TG / DTA, the sample was heated from room temperature to 250 ± 3 ° C. at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere, held for 1 hour, Measure. The weight reduction rate is determined from the initial weight and the weight after heating.

  The phosphorus-containing compound preferably includes a structure represented by the following formula (3).

式（３）中、Ｒ¹⁷およびＲ¹⁸は、それぞれ独立に炭素原子数１〜２０の炭化水素基を表し、Ａｒは芳香族基を表し、ｍ+ｎ＝０〜３の整数、あるいはｍは２または３、ｎは０または１を表す。

In the formula (3), R ¹⁷ and R ¹⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, Ar represents an aromatic group, m + n = 0 to 3 or an integer of m 2 or 3, n represents 0 or 1.

  Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, and a t-butyl group. In addition, the hydrogen atom of these alkyl groups may be substituted with other substituents, and in particular, substitution with a hindered phenol group is preferable because coloring can be sufficiently suppressed. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Moreover, the hydrogen atom of these aryl groups may be substituted with other substituents. For example, the compound represented by the above formula (3) and the target structure via a biphenylene group like the compound represented by the following formula (4) May be formed. Such a structure is preferable because the volatility can be reduced by increasing the molecular weight while maintaining the effect of the phosphorus antioxidant.

芳香族基としては、例えば、フェニル基、ナフチル基およびアントラセニル基などが挙げられ、好ましくはフェニル基が挙げられる。これらの芳香族基の水素原子は他の置換基で置換されていてもよく、特にｔ−ブチル基などの嵩高い基で置換されていると、耐加水分解性および耐熱性が向上するため好ましい。また、上記芳香族基はＲ¹⁸と直接または置換基を介して結合してもよい。

As an aromatic group, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example, Preferably a phenyl group is mentioned. The hydrogen atom of these aromatic groups may be substituted with other substituents, and particularly when substituted with a bulky group such as a t-butyl group, it is preferable because hydrolysis resistance and heat resistance are improved. . The aromatic group may be bonded to R ¹⁸ directly or via a substituent.

  Specific examples of the phosphorus-containing compound (C) include tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenedi. Mixtures mainly composed of phosphonite (for example, Clariant Japan Co., Ltd .; Hostanox P-EPQ), tetrakis (2,4-di-t-butylphenyl-5-methyl) -4,4'-biphenylenediphospho A mixture containing knight as a main component (eg, Osaki Kogyo Co., Ltd .; GSY-P101), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8 , 10-Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-Dicumylphenyl) pentaerythritol diphosphite. Of these, tris (2,4-di-t-butylphenyl) phosphite represented by the formula (3-a) and formula (3-b) are particularly preferable in terms of low volatility and low colorability. 6- [3- (3-t-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] di And oxaphosphepine and tetrakis (2,4-di-t-butylphenyl-5-methyl) -4,4′-biphenylenediphosphonite represented by the formula (3-c).

  These phosphorus-containing compounds (C) can be used alone or in combination of two or more. When two or more types are used in combination, it is particularly preferable to use a compound represented by the formula (3-a), (3-b) or (3-c) as a main component.

含リン化合物（Ｃ）の添加量は、環状オレフィン系樹脂（Ａ）１００重量部に対して、好ましくは０．００５〜５重量部、より好ましくは０．００７〜４重量部、特に好ましくは０．０１〜３重量部である。含リン化合物（Ｃ）の添加量が上記の範囲にあると、樹脂組成物の色相を良好に保ち、ゲル生成を防止し、かつ、発煙および発塵を最低限に抑制することができる。

The amount of the phosphorus-containing compound (C) added is preferably 0.005 to 5 parts by weight, more preferably 0.007 to 4 parts by weight, and particularly preferably 0 with respect to 100 parts by weight of the cyclic olefin resin (A). 0.01 to 3 parts by weight. When the addition amount of the phosphorus-containing compound (C) is in the above range, the hue of the resin composition can be kept good, gel formation can be prevented, and smoke and dust can be minimized.

  When the phosphorus-containing compound (C) is used in combination, the hue improving effect is recognized even when the content of the phenolic compound (B) is reduced. Therefore, the quality balance can be controlled by the required characteristics.

[Resin composition]
The resin composition of the present invention can be produced by melt-kneading the cyclic olefin resin (A), the phenol compound (B) and, if necessary, the phosphorus-containing compound (C).

In the resin composition, the light stabilizer, the ultraviolet absorber, the infrared absorber, the antistatic agent, the dispersant, the processability improver, the chlorine scavenger, the flame retardant, and the crystal are provided as long as the effects of the present invention are not impaired. Nucleating agent, antiblocking agent, antifogging agent, mold release agent, dye, pigment, fluorescent whitening agent, organic filler, inorganic filler, neutralizer, lubricant, decomposition agent, metal deactivator, antifouling Known additives such as materials and antibacterial agents and resins such as thermoplastic elastomers can be added.
For melt kneading, a kneading apparatus such as a kneading and dispersing machine such as a roll kneader, a mixer, a homomixer, or a sand mill is used.

[Optical parts]
Since the resin composition of the present invention has high transparency, low colorability, and high heat resistance, it can be used in electronic and optical materials such as optical films, optical disks, optical lenses, optical fibers, transparent plastic substrates and low dielectric materials, and optical semiconductors. Suitable for sealing materials and the like.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
The analysis methods used in Examples and Comparative Examples are shown below.

<Analysis method>
(1) GPC: Gel permeation chromatograph apparatus (HLC-8220GPC manufactured by Tosoh Corporation, column; guard column HXL-H, TSK gel G7000HXL, two TSK gel GMHXL, TSK gel G2000HXL manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8 wt%, sample injection volume: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard substance: TSK manufactured by Tosoh Corporation Standard polystyrene) was used to measure the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) in terms of standard polystyrene. In addition, Mn is the number average molecular weight of standard polystyrene conversion.
(2) NMR: ¹ H-NMR was measured in deuterated chloroform using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500), and the copolymer composition ratio and hydrogenation rate were determined. Asked.
(3) Logarithmic viscosity: Measured using a Ubbelohde viscometer in chloroform at a sample concentration of 0.5 g / dL and a temperature of 30 ° C.
(4) Glass transition temperature (Tg): Extrapolated glass transition temperature was determined according to Japanese Industrial Standard K7121 using a differential scanning calorimeter (trade name: DSC6220, manufactured by SII Nano Technology).
(5) Scanning electron microscope: JSM6360LA type manufactured by JEOL Ltd. was used.

[Synthesis Example 1]
As a monomer, 8-methoxycarbonyl-8-methyltetracyclo represented by the following formula (1-a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (100 g), 1-hexene (7.2 g) as a molecular weight regulator, and toluene (200 g) were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C.

To this, 0.21 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 0.86 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl ₆ ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opened polymer was obtained.

0.04 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ) as a hydrogenation catalyst was added to the resulting ring-opening polymer solution, and hydrogen gas The pressure was 9 to 10 MPa and the reaction was carried out at 160 to 165 ° C. for 3 hours.

After completion of the reaction, the resulting reaction mixture was precipitated in a large amount of methanol to obtain a hydrogenated product. This hydrogenated product is referred to as 1A.
The yield of the obtained hydrogenated product (1A) was 90 g (yield 90%), the glass transition temperature (Tg) was 163 ° C., the weight average molecular weight (Mw) was 6.7 × 10 ⁴ , and the molecular weight distribution (Mw / Mn ) Was 5.0, the logarithmic viscosity was 0.45 dL / g, and the hydrogenation rate was 99.0% or more.

[合成例２]
式（１−ａ）に示す８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン１４４ｇ、式（１−ｂ）に示す２−ノルボルネン６ｇ、分子量調節剤として１−へキセン１４．４ｇおよびトルエン２２５ｇを窒素置換した反応容器に仕込み、８０℃に加熱した。

[Synthesis Example 2]
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (144 g), 2-norbornene (6 g) represented by formula (1-b), 1-hexene (14.4 g) and molecular weight regulator (14.4 g) and toluene (225 g) were charged into a reaction vessel purged with nitrogen and heated to 80 ° C. Heated.

To this, 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl ₆ ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.

To the obtained ring-opening copolymer solution, 0.06 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ) as a hydrogenation catalyst was added, and hydrogen was added. The gas pressure was 9 to 10 MPa and the reaction was carried out at 160 to 165 ° C. for 3 hours.

After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. This hydrogenated product is referred to as 2A.
The yield of the obtained hydrogenated product (2A) was 90 g (yield 90%), the glass transition temperature (Tg) was 154 ° C., the weight average molecular weight (Mw) was 7.4 × 10 ⁴ , and the molecular weight distribution (Mw / Mn ) Is 4.2, logarithmic viscosity is 0.55 dL / g, hydrogenation rate is 99.0% or more, copolymer composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] Was 95.8 / 4.2 (weight ratio).

[合成例３]
式（１−ａ）に示す８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン１１３．２ｇ、式（１−ｂ）に示す２−ノルボルネン１．５ｇ、下記式（１−ｃ）に示すジシクロペンタジエン３５．３ｇ、分子量調節剤として１−へキセン２０．５ｇおよびトルエン２２５ｇを窒素置換した反応容器に仕込み、８０℃に加熱した。

[Synthesis Example 3]
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 113.2 g, 1.5 g of 2-norbornene represented by the formula (1-b), 35.3 g of dicyclopentadiene represented by the following formula (1-c), 1- A reaction vessel purged with nitrogen of 20.5 g of hexene and 225 g of toluene was charged and heated to 80 ° C.

To this, 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.39 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl ₆ ) (0.025 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.

(4-Pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO—Ar—CH ₂ CH ₂ CH ₂ CH ₂ CH) as a hydrogenation catalyst was added to the obtained ring-opening copolymer solution. ₃ ) 0.06 g of (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) was added, the temperature was raised to 90 ° C., and the hydrogen gas pressure was adjusted to 9 to 10 MPa. Furthermore, the temperature was raised to 160 to 165 ° C. and the reaction was carried out for 3 hours. This hydrogenated product is referred to as 3A.

The obtained hydrogenated product (3A) had a yield of 90 g (yield 90%), a glass transition temperature (Tg) of 141 ° C., a weight average molecular weight (Mw) of 4.4 × 10 ⁴ , and a molecular weight distribution (Mw / Mn). ) Is 5.1, logarithmic viscosity is 0.41 dL / g, hydrogenation rate is 99.0% or more, copolymer composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] / [Structure derived from (1-c)] was 75.3 / 1.1 / 23.6 (weight ratio).

[合成例４]
前記式（１−ａ）に示す８−メトキシカルボニル−８−メチルテトラシクロ［４．４．０．１^2,5．１^7,10］−３−ドデセン１３３．５ｇ、前記式（１−ｂ）に示す２−ノルボルネン１６.５ｇ、分子量調節剤として１−へキセン１５．４ｇ、およびトルエン２２５ｇを窒素置換した反応容器に仕込み、８０℃に加熱した。

[Synthesis Example 4]
8-methoxycarbonyl-8-methyltetracyclo represented by the above formula (1-a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (133.5 g), 2-norbornene (16.5 g) represented by the formula (1-b), 15.4 g of 1-hexene as a molecular weight regulator, and 225 g of toluene were substituted with nitrogen. And heated to 80 ° C.

To this was added 0.34 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of a methanol-modified WCl ₆ toluene solution (0.025 mol / L), and the mixture was reacted at 80 ° C. for 1 hour to open the ring. A copolymer was obtained.

Next, 0.06 g of chlorohydridocarbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ) as a hydrogenation catalyst was added to the obtained ring-opening copolymer solution. The hydrogen gas pressure was 9 to 10 MPa, and the reaction was performed at a temperature of 160 to 165 ° C. for 3 hours.

After completion of the reaction, the product obtained was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 126 ° C., weight average molecular weight (Mw) = 5.0 × 10 ⁴ , Molecular weight distribution (Mw / Mn) = 4.2, logarithmic viscosity 0.43 dL / g, yield 90 g (90% yield)]. The hydrogenation rate of the hydrogenated product determined by NMR measurement is 99.0% or more, and the copolymer composition ratio is [structure derived from (1-a)] / [structure derived from (1-b)] = 89. / 11 (weight ratio). Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 4A.

[Synthesis Example 5]
8-methoxycarbonyl-8-methyltetracyclo represented by the formula (1-a) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 42.0 g, 1,4,4a, 9a-tetrahydro-1,4-methanofluorene 28.0 g represented by the following formula (1-d), 1-hexene as a molecular weight regulator 11.2 g and 105 g of toluene were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C.

To this, 1.15 mL of a toluene solution of triethylaluminum (0.2 mol / L) and 0.67 mL of a toluene solution of methanol-modified tungsten hexachloride (WCl ₆ ) (0.050 mol / L) are added and reacted at 80 ° C. for 1 hour. As a result, a ring-opening copolymer was obtained.

The resulting ring-opening copolymer solution was diluted by adding 251 g of toluene, and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ ) as a hydrogenation catalyst. 0.02 g of CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, the hydrogen gas pressure is adjusted to 9 to 10 MPa, The temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 5A.

After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product [glass transition temperature (Tg) = 161 ° C., weight average molecular weight (Mw) = 8.3 × 10 ⁴ , Molecular weight distribution (Mw / Mn) = 3.8, logarithmic viscosity 0.51 dL / g, yield 63 g (yield 90%)]. The hydrogenation rate of this hydrogenated product determined by NMR measurement is 99.0% or more, and the copolymer composition ratio is [structure derived from (1-a)] / [structure derived from (1-d)] = 59. / 41 (weight ratio). Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 5A.

[合成例６]
上記式（１−ｃ）に示すジシクロペンタジエン４５．０ｇ、分子量調節剤として１−へキセン０．３ｇおよびシクロヘキサン１０３ｇを窒素置換した反応容器に仕込み、７０℃に加熱した。

[Synthesis Example 6]
A reaction vessel purged with nitrogen of 45.0 g of dicyclopentadiene represented by the above formula (1-c), 0.3 g of 1-hexene and 103 g of cyclohexane as a molecular weight regulator was charged and heated to 70 ° C.

To this, 0.51 mL of a toluene solution of triisobutylaluminum (1.0 mol / L), 0.51 mL of a cyclohexane solution of 2-butanol (1.0 mol / L), 1.70 ml of a toluene solution of acetone (0.1 mol / L) Then, 6.81 mL of a toluene solution (0.025 mol / L) of tungsten hexachloride (WCl ₆ ) was added and reacted at 70 ° C. for 1 hour to obtain a ring-opening copolymer.

The obtained ring-opening copolymer solution was diluted by adding 456.4 g of cyclohexane and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-) as a hydrogenation catalyst. 0.05 g of CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, and the hydrogen gas pressure is adjusted to 9 to 10 MPa. Further, the temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 6A.

After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. The yield of the obtained hydrogenated product (6A) was 40 g (yield 89%), and the glass transition temperature (Tg) was 100 ° C. The molecular weight was measured by measuring GPC using o-dichlorobenzene. The weight average molecular weight (Mw) was 6.8 × 10 ⁴ , the molecular weight distribution (Mw / Mn) was 1.8, and the hydrogenation rate was 99.0% or more. Hereinafter, the obtained ring-opening copolymerized hydrogenated product is referred to as a cyclic olefin-based resin 6A.

[Synthesis Example 7]
31.5 g of dicyclopentadiene represented by the above formula (1-c), and tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 38.5 g, 0.4 g of 1-hexene as a molecular weight regulator and 165 g of cyclohexane were charged into a nitrogen-substituted reaction vessel and heated to 70 ° C.

To this, 0.96 mL of a toluene solution of triisobutylaluminum (1.0 mol / L), 0.72 mL of a cyclohexane solution of 2-butanol (1.0 mol / L), 2.39 ml of a toluene solution of acetone (0.1 mol / L) Then, 9.57 mL of a toluene solution (0.025 mol / L) of tungsten hexachloride (WCl ₆ ) was added and reacted at 70 ° C. for 1 hour to obtain a ring-opening copolymer.

The resulting ring-opening copolymer solution was diluted by adding 633 g of cyclohexane and (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ ) as a hydrogenation catalyst. 0.04 g of CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, the hydrogen gas pressure is adjusted to 9-10 MPa, The temperature was raised to 160 to 165 ° C. and reacted for 3 hours. This hydrogenated product is referred to as 7A.

After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a hydrogenated product. The yield of the obtained hydrogenated product (7A) was 65 g (yield 93%), and the glass transition temperature (Tg) was 130 ° C. The molecular weight was measured by measuring GPC using o-dichlorobenzene. The weight average molecular weight (Mw) was 4.5 × 10 ⁴ , the molecular weight distribution (Mw / Mn) was 2.7, and the hydrogenation rate was 99.0% or more. The copolymer composition ratio was [structure derived from (1-c)] / [structure derived from (1-de)] = 46/54 (weight ratio). Hereinafter, the obtained hydrogenated ring-opening copolymer is referred to as a cyclic olefin resin 7A.

［実施例１］
合成例１で得られた水素添加体（１Ａ）１００ｇに対して、フェノール系化合物（Ｂ）として式（２−ａ）に示す1,1,3-トリス[2-メチル-4-[3-（3,5-ジ-t-ブチル-4-ヒドロキシフェニル）プロピオニルオキシ]-5-t-ブチルフェニル]ブタンを０．３ｇ添加してラボプラストミルにて空気下、２８０℃で３０分間混練し、樹脂組成物を得た。

[Example 1]
For 1,100 g of the hydrogenated product (1A) obtained in Synthesis Example 1, 1,1,3-tris [2-methyl-4- [3-] represented by the formula (2-a) as the phenol compound (B) 0.3 g of (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane was added and kneaded for 30 minutes at 280 ° C. under air in a lab plast mill. A resin composition was obtained.

  In addition, the property of the used phenol type compound (B) is shown in Table 1, and the preparation conditions of a resin composition are shown in Table 2.

［実施例２］
実施例１において、水素添加体（１Ａ）の代わりに、合成例２で得られた水素添加体（２Ａ）を用いたこと以外は実施例１と同様にして樹脂組成物を得た。

[Example 2]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (2A) obtained in Synthesis Example 2 was used instead of the hydrogenated product (1A).

[Example 3]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (3A) obtained in Synthesis Example 3 was used instead of the hydrogenated product (1A).

[Example 4]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the amount of the compound represented by the formula (2-a) was changed from 0.3 g to 1.0 g.

[Example 5]
In Example 3, in addition to the hydrogenated compound (3A) and the compound represented by the formula (2-a), tris (2,4-di- A resin composition was obtained in the same manner as in Example 3 except that 0.3 g of t-butylphenyl) phosphite was added.
The properties of the phosphorus-containing compound (C) used are shown in Table 1.

［実施例６］
実施例５において、式（３−ａ）に示す化合物の代わりに、下記式（３−ｂ）に示す6-[3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-2,4,8,10-テトラ-t-ブチルジベンズ［d,f］［1,3,2］ジオキサホスフェピンを用いたこと以外は実施例５と同様にして樹脂組成物を得た。

[Example 6]
In Example 5, instead of the compound represented by the formula (3-a), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy represented by the following formula (3-b) A resin composition was obtained in the same manner as in Example 5 except that -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine was used. .

  The properties of the phosphorus-containing compound (C) used are shown in Table 1.

［実施例７］
実施例５において、式（３−ａ）に示す化合物の代わりに、下記式（３−ｃ）に示すテトラキス（2,4-ジ-t-ブチル-5-メチルフェニル）-4,4'-ビフェニレンジホスホナイトを主成分とするリン系酸化防止剤（商品名；大崎工業（株）製ＧＳＹ−Ｐ１０１）を用いたこと以外は実施例５と同様にして樹脂組成物を得た。

[Example 7]
In Example 5, instead of the compound represented by the formula (3-a), tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′- represented by the following formula (3-c) A resin composition was obtained in the same manner as in Example 5 except that a phosphorus-based antioxidant (trade name; GSY-P101 manufactured by Osaki Kogyo Co., Ltd.) mainly containing biphenylene diphosphonite was used.

  The properties of the phosphorus-containing compound (C) used are shown in Table 1.

[実施例８]
合成例４で得られた水素添加体（４Ａ）１００ｇに対して、フェノール系化合物（Ｂ）として前記式（２−ａ）に示す1,1,3-トリス[2-メチル-4-[3-（3,5-ジ-t-ブチル-4-ヒドロキシフェニル）プロピオニルオキシ]-5-t-ブチルフェニル]ブタンを３ｇ添加してラボプラストミルにて空気下、２６０℃で３０分間混練し、樹脂組成物を得た。

[Example 8]
With respect to 100 g of the hydrogenated product (4A) obtained in Synthesis Example 4, 1,1,3-tris [2-methyl-4- [3] represented by the above formula (2-a) as a phenol compound (B) 3 g of-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane was added and kneaded at 260 ° C. for 30 minutes in the air with a lab plast mill. A resin composition was obtained.

[Example 9]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (5A) obtained in Synthesis Example 5 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.

[Example 10]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (6A) obtained in Synthesis Example 6 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.

[Example 11]
In Example 1, a resin composition was obtained in the same manner as in Example 1 except that the hydrogenated product (7A) obtained in Synthesis Example 7 was used instead of the hydrogenated product (1A).
In addition, it shows in Table 3 about preparation of a resin composition.

[Comparative Example 1]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-a) was used instead of the compound represented by the formula (2-a).

  The properties of the compound represented by the formula (2′-a) are shown in Table 1, and the preparation of the resin composition is shown in Table 2.

［比較例２］
実施例４において、式（２−ａ）に示す化合物１．０ｇの代わりに、式（２'−ａ）に示す化合物１．５ｇを用いたこと以外は実施例４と同様にして樹脂組成物を得た。

[Comparative Example 2]
In Example 4, a resin composition was obtained in the same manner as in Example 4 except that 1.5 g of the compound represented by the formula (2′-a) was used instead of 1.0 g of the compound represented by the formula (2-a). Got.

[Comparative Example 3]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-b) was used instead of the compound represented by the formula (2-a).

  In addition, Table 1 shows properties of the compound represented by the formula (2′-b).

［比較例４］
実施例３において、式（２−ａ）に示す化合物の代わりに、下記式（２'−ｃ）に示す化合物を用いたこと以外は実施例３と同様にして樹脂組成物を得た。

[Comparative Example 4]
In Example 3, a resin composition was obtained in the same manner as in Example 3 except that the compound represented by the following formula (2′-c) was used instead of the compound represented by the formula (2-a).

  In addition, Table 1 shows properties of the compound represented by the formula (2′-c).

＜評価方法＞
実施例および比較例で得られた樹脂組成物について以下の評価を行った。結果を表２および３に示す。
（１）発煙性評価：プラストミル混練時の発煙性を下記の基準で目視観察した。
○ 発煙しなかった
△ ほとんど発煙しなかった
× 発煙した

<Evaluation method>
The following evaluation was performed about the resin composition obtained by the Example and the comparative example. The results are shown in Tables 2 and 3.
(1) Evaluation of smoke generation: The smoke generation during plastmill kneading was visually observed according to the following criteria.
○ No smoke △ Almost no smoke × No smoke

(2) Hue evaluation: The resin composition was dissolved in toluene to obtain a solution having a concentration of 10% by weight, and the yellowness (YI) was measured and evaluated. The measurement was performed using a SM color computer SM-7-CH manufactured by Suga Test Instruments Co., Ltd., and C-light 2 ° visual field transmission measurement was performed three times to obtain an average value (measurement sample: using 20 g of sample solution, measurement cell: A cylindrical glass cell having an inner diameter of 60 mm and a height of 30 mm).

(3) Gel evaluation: The resin composition was dissolved in toluene to obtain a solution having a concentration of 10% by weight, and then filtered through a PTFE filter having a pore size of 1.0 μm. After filtration, the filter is baked at 260 ° C. for 30 minutes in the air to cause toluene insoluble component (gel) remaining on the filter to oxidize and develop color (brown). The number of gels in 1 g of the resin composition was calculated from the filtration amount, and less than 100 pieces / g was evaluated as ○ and 500 pieces / g or more as x. The gel is an organic substance that exists in a plane on the filter and has been browned by firing, and those having a fiber shape and three-dimensional shape were not counted as the number of gels as foreign substances derived from the environment.

(4) Transparency evaluation: The transparency of the resin composition obtained by plastmill kneading was visually observed according to the following criteria.
○ It was transparent △ Slightly cloudy × Cloudy From the results in Table 2, a resin composition obtained by adding a specific phenol compound (B) to a cyclic olefin resin (A) has been conventionally regarded as a problem. It can be seen that all the problems such as coloring during processing, gel formation and fuming can be improved. Further, for example, from the comparison results of Examples 4 and 7, when the phosphorus-containing compound (C) is used in combination, the hue improving effect is recognized even when the amount of the phenolic compound (B) is reduced, so that the required characteristics are obtained. Can control the quality balance.

Claims (8)

Cyclic olefin resin (A) having a structural unit derived from a compound represented by the following formula (1) and a phenolic compound (B) having two or more groups represented by the following formula (2) in one molecule The cyclic olefin resin (A) is obtained by hydrogenating a ring-opening (co) polymer of the compound represented by the formula (1). A resin composition, wherein the resin is a ring-opening polymer (A-2) and the phenol compound (B) is a compound represented by the following formula (2-1).

(In the formula (1), a and b each independently represent 0 or 1, c and d each independently represent an integer of 0 to 2. R ^{4 to} R ¹³ each independently represents a hydrogen atom; a halogen atom. A hydrocarbon group having 1 to 30 carbon atoms which may be linked by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, or other polar group, R ¹⁰ and R ¹¹ , or R ¹² And R ¹³ may be combined to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ are bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring. A ring may be formed.)

(In the formula (2), R ^14a and R ^14b are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently 1 carbon atom. -10 hydrocarbon group, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms.)

(In formula (2-1), R ^14a and R ^14b are each independently a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ are each independently a carbon atom. A hydrocarbon group having 1 to 10 carbon atoms, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms, Y is an n-valent group, a chain hydrocarbon group having 3 to 12 carbon atoms or a carbon atom Represents a cyclic hydrocarbon group of formula 4-8, n is an integer of 2-4.) The resin composition according to claim 1, wherein the compound represented by the formula (2-1) satisfies the following requirements (B-i) and (B-ii).
(B-i): molecular weight is 800 or more (B-ii): weight loss rate when heated at 300 ° C. for 1 hour under nitrogen is 15% or less The resin composition according to claim 1 or 2, wherein the compound represented by the formula (2-1) is a compound represented by the following formula (2-a).

Furthermore, it contains a phosphorus-containing compound (C) that satisfies the following requirements (Ci) and (C-ii):
The phosphorus-containing compound (C) is at least one selected from compounds represented by the following formulas (3-a) to (3-c) , and the phosphorus-containing compound (C) is a cyclic olefin resin. (A) 0.005-5 weight part is contained with respect to 100 weight part, The resin composition in any one of Claims 1-3 characterized by the above-mentioned.
(Ci): The relative molecular mass of a single compound is 400 or more, and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) in a polydisperse mixture.
) Is 400 or more,
(C-ii): Weight reduction rate when heated at 250 ° C. for 1 hour under nitrogen is 50% or less

  The weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the ring-opening (co) polymerized hydrogenated product (A-2) is 30,000 to 200,000. The resin composition as described.   The resin composition according to claim 1 or 5, wherein the ring-opening (co) polymerized hydrogenated product (A-2) has a glass transition temperature (Tg) of 100 to 250 ° C.   6. The hydrogenation rate of a carbon-carbon double bond excluding an unsaturated bond of an aromatic ring of the ring-opening (co) polymerized hydrogenated product (A-2) is 90% or more. Or the resin composition of 6.   An optical component comprising the resin composition according to claim 1.