JP2010037349A - Resin composition and its molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which retains desirable transparency, heat resistance and mechanical properties inherent in a cyclic polyolefin resin, and exhibits excellent flame retardancy, when molded. <P>SOLUTION: The resin composition comprises (i) 60-99 pts.wt. of a resin component including a cyclic polyolefin resin (A) and (ii) 1-40 pts.wt. of a flame retardant (in which the total of (i) and (ii) is 100 pts.wt.), wherein the flame retardant (ii) comprises (ii-1) a compound (B) having a phosphorus atom and a halogen atom in the same molecule, (ii-2) a phosphorus compound (C) and a halogen compound (D), (ii-3) the compound (B) and the compound (C), (ii-4) the compound (B) and the compound (D), or (ii-5) the compound (B), the compound (C) and the compound (D). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition containing a cyclic polyolefin resin. More specifically, the present invention relates to a resin composition containing a cyclic polyolefin resin and a specific flame retardant, and a molded article obtained by molding the composition.

In recent years, hydrogenated cyclic olefin ring-opening polymers are excellent in transparency, heat resistance, and the like, and therefore are increasingly used as materials for electrical and electronic parts including optical materials.
However, since the hydrogenated cyclic olefin ring-opening polymer is easily combusted, its use as a sealing material, protective film material, insulating material, etc. for electric / electronic parts has been restricted from the viewpoint of safety.

  In order to impart flame retardancy to the hydrogenated cyclic olefin ring-opening polymer, a resin obtained by combining a hydrogenated cyclic olefin ring-opening polymer and one or more flame retardants in combination. Compositions have been proposed.

  For example, halogen flame retardant, antimony flame retardant, magnesium hydroxide (Patent Document 1), ammonium polyphosphate (Patent Document 2), low molecular weight or high molecular weight halogen organic flame retardant, inorganic compound flame retardant such as antimony oxide A resin composition combined with a phosphorus-based flame retardant (Patent Document 3) has been proposed.

  However, the above-described composition has a problem that flame retardancy is improved, but properties such as preferable transparency inherent in the hydrogenated cyclic olefin ring-opening polymer are impaired. In addition, there has been a problem that the use of antimony flame retardants is not preferred due to an increase in concern about safety for the human body.

And the resin composition which combined and combined the hydrogenated cyclic olefin ring-opening polymer and a specific condensed type phosphate ester compound was proposed (patent document 4). However, there is room for improvement in flame retardancy while maintaining the preferable transparency, heat resistance, and mechanical properties inherent to such a cyclic olefin-based ring-opening polymer.
JP-A-2-255848 JP-A-5-239284 JP-A-11-140282 JP 2006-328175 A

  An object of the present invention is to provide a resin composition excellent in flame retardancy while maintaining the preferable transparency, heat resistance and mechanical properties inherent in cyclic polyolefin resins when molded.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have obtained a specific cyclic polyolefin resin, a compound having a phosphorus atom and a halogen atom in the same molecule, a phosphorus compound and / or a halogen compound. The present invention is completed by finding that a cyclic olefin resin composition having excellent transparency, heat resistance and mechanical properties and excellent flame retardancy can be obtained by containing a specific combination and a specific ratio. It came to do.

That is, the resin composition of the present invention is
(I) 60 to 99 parts by weight of a resin component containing the cyclic polyolefin resin (A);
(Ii) 1 to 40 parts by weight of a flame retardant (however, the total of the following (i) and the following (ii) is 100 parts by weight), and the flame retardant (ii)
(Ii-1) Compound (B) containing a phosphorus atom and a halogen atom in the same molecule,
(Ii-2) phosphorus compound (C) and halogen compound (D),
(Ii-3) The compound (B) and the compound (C),
(Ii-4) The compound (B) and the compound (D), or (ii-5) the compound (B), the compound (C) and the compound (D).

  The flame retardant (ii-2) comprises 5 to 50% by weight of the phosphorus compound (C) and 50 to 95% by weight of the halogen compound (D) (provided that the compound (C), the compound (D), It is preferable to include 100% by weight.

  The flame retardant (ii-3) comprises 60 to 98% by weight of the compound (B) containing a phosphorus atom and a halogen atom in the same molecule, and 2 to 40% by weight of the compound (C) (however, the compound (B) B) and the total amount of the compound (C) are preferably 100% by weight).

  The flame retardant (ii-4) comprises 15 to 60% by weight of the compound (B) and 40 to 85% by weight of the compound (D) (provided that the total of the compound (B) and the compound (D) Is preferably 100% by weight).

  The flame retardant (ii-5) comprises 10 to 50% by weight of the compound (B), 5 to 45% by weight of the compound (C), and 5 to 45% by weight of the compound (D). (B), the compound (C), and the compound (D) are preferably included in an amount of 100% by weight).

The glass transition temperature [Tg] is preferably 80 ° C. or higher.
The compound (B) is preferably a compound represented by the following formula (1).

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、置換基を有していてもよい炭素原子数
１〜２０の炭化水素基または極性基を表し、Ｒ¹〜Ｒ³の少なくとも１つは、ハロゲン原子を含む。）
上記樹脂（Ａ）は、下記式（２）で表される単量体から導かれる構造単位を有する（共）重合体であることが好ましい。

(In the formula, R ¹ , R ² and R ³ each independently represents a hydrocarbon group or polar group having 1 to 20 carbon atoms which may have a substituent, and at least ^one of R ^{1 to} R ³ One contains a halogen atom.)
The resin (A) is preferably a (co) polymer having a structural unit derived from a monomer represented by the following formula (2).

（式（２）中、Ｒ⁴〜Ｒ⁷は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基またはその他の１価の有機基を表し、Ｒ⁴〜Ｒ⁷のうち任意の２つは、互いに結合して単環または多環を形成してもよい。ｍおよびｎは、それぞれ独立に、０または正の整数を表す。）
上記リン系化合物（Ｃ）は、下記式（３）で表される化合物であることが好ましい。

(In the formula (2), R ^{4 to} R ⁷ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms or other monovalent organic group, and R ^{4 to} R ⁷ Any two of them may be bonded to each other to form a monocycle or polycycle, and m and n each independently represents 0 or a positive integer.)
The phosphorus compound (C) is preferably a compound represented by the following formula (3).

（式（３）中、Ｒ⁸、Ｒ⁹およびＲ¹¹〜Ｒ¹³は、それぞれ独立に、炭素原子数５〜２０のアリール基を表し、Ｒ¹⁰は、炭素原子数６〜２５のアリーレン基を表し、ｎは、１〜３の整数を表す。）
上記ハロゲン系化合物（Ｄ）は、下記式（４）で表される化合物であることが好ましい。

(In the formula (3), R ⁸ , R ⁹ and R ^{11 to} R ¹³ each independently represents an aryl group having 5 to 20 carbon atoms, and R ¹⁰ represents an arylene group having 6 to 25 carbon atoms. And n represents an integer of 1 to 3.)
The halogen compound (D) is preferably a compound represented by the following formula (4).

（式（４）中、Ｘは、ハロゲン原子またはハロゲン原子を含む炭素原子数１〜１０の炭化水素基を表し、Ｙは、５〜１２員環を表し、Ｒ¹⁴は、酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有してもよい置換または非置換の炭素原子数１〜２０の炭化水素基；または極性基を表し、ｍは、１〜１０の整数を表し、ｌとｎとの和は、Ｙを表す環を形成する炭素原子数と同数を表し、ｌおよびｎは、それぞれ１以上の整数を表す。）
また、本発明の成形体は、本発明の樹脂組成物を用いて形成されることを特徴とするものであって、光学部品用に好適であり、該光学部品の形状は、フィルム状、シート状またはレンズ状であることが好ましい。

(In the formula (4), X represents a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms including a halogen atom, Y represents a 5- to 12-membered ring, and R ¹⁴ represents an oxygen atom or a sulfur atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may have a linking group containing a nitrogen atom or a silicon atom; or represents a polar group, m represents an integer of 1 to 10; And n represents the same number as the number of carbon atoms forming the ring representing Y, and l and n each represents an integer of 1 or more.)
In addition, the molded article of the present invention is characterized by being formed using the resin composition of the present invention, and is suitable for an optical component. The shape of the optical component is a film or sheet. The shape is preferably a lens shape or a lens shape.

The resin composition of the present invention is excellent in transparency, heat resistance and mechanical properties, and is excellent in flame retardancy.
Accordingly, a molded body such as a film formed from the resin composition of the present invention is suitably used as a material for electrical and electronic parts as well as optical parts.

Next, the present invention will be specifically described.
<Resin composition>
The resin composition of the present invention comprises (i) 60 to 99 parts by weight of a resin component containing a cyclic polyolefin resin (A), (ii) 1 to 40 parts by weight of a flame retardant (however, the following (i) and ( ii) is 100 parts by weight), and the flame retardant (ii)
(Ii-1) Compound (B) containing a phosphorus atom and a halogen atom in the same molecule,
(Ii-2) phosphorus compound (C) and halogen compound (D),
(Ii-3) The compound (B) and the compound (C),
(Ii-4) The compound (B) and the compound (D), or (ii-5) the compound (B), the compound (C) and the compound (D). .

[Cyclic polyolefin resin (A)]
The cyclic polyolefin resin (A) used in the present invention is a (co) polymer having a structural unit derived from a monomer represented by the following formula (2) (hereinafter also referred to as “specific monomer”). The specific monomer includes the following (co) polymers.

（式（２）中、Ｒ⁴〜Ｒ⁷は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜３０の炭化水素基またはその他の１価の有機基を表し、Ｒ⁴〜Ｒ⁷のうち任意の２つは、互いに結合して単環または多環を形成してもよい。ｍおよびｎは、それぞれ独立に、０または正の整数を表す。）

(In the formula (2), R ^{4 to} R ⁷ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms or other monovalent organic group, and R ^{4 to} R ⁷ Any two of them may be bonded to each other to form a monocycle or polycycle, and m and n each independently represents 0 or a positive integer.)

(I) A ring-opening (co) polymer of a specific monomer.
(II) A ring-opening copolymer of a specific 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 copolymer of a specific monomer and an unsaturated double bond-containing compound.
(VI) Addition type (co) polymers of one or more monomers selected from specific monomers, vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and their hydrogenated (co) weights Coalescence.
(VII) An alternating copolymer of a specific monomer and an acrylate.
Of these, the hydrogenated (co) polymers of the polymers (III) to (VI), which are excellent in both optical properties and processing properties, are preferred, and in particular, the hydrogenation of the ring-opened (co) polymer of (III) ( Co) polymers are preferred.

(Specific monomer)
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -3-decene,
Tricyclo [4.3.0.1 ^2,5 ] -decane-3,8-diene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [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-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-n-butoxycarbonyltetracyclo [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-methyl-8-ethoxycarbonyltetracyclo [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-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene,

5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
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-pentafluoroethylbicyclo [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,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [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,

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-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-pentafluoroethyltetracyclo [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,
8,9-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-bis (trifluoromethyl) tetracyclo [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,
8,8,9-trifluorotetracyclo [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,
8,8,9,9-tetrafluorotetracyclo [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-difluoro-9,9-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,
8,8,9-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-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [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,
8,9-dichloro-8,9-bis (trifluoromethyl) 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-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Spiro [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene]
And so on. These can be used alone or in combination of two or more.

Among the specific monomers, in the above formula (2), R ⁴ and R ⁶ are each a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms. And R ⁵ and R ⁷ are a hydrogen atom or a monovalent organic group. It is desirable that at least one of R ⁵ and R ⁷ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group. m and n are each independently an integer of 0 to 3, more preferably m + n = 0 to 4, more preferably 0 to 2, particularly preferably m = 0 and n = 1. The specific monomer with m = 0 and n = 1 is preferable in that the obtained cyclic polyolefin resin has a high glass transition temperature [Tg] and excellent mechanical strength.

  Examples of the “polar group” of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups are linking groups such as a methylene group. It may be connected via. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ⁵ and R ⁷ is a polar group represented by the formula: — (CH ₂ ) _p COOR is obtained by using a cyclic polyolefin-based resin having a high glass transition temperature, a low hygroscopic property, It is preferable at the point which has the outstanding adhesiveness with material. In the formula relating to the above specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. Moreover, p is usually 0 to 5, but the smaller the value of p, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer whose p is 0 is It is preferable in that the synthesis is easy.

In the above formula (2), R ⁴ or R ⁶ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly a methyl group. In particular, it is preferable that the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the formula: — (CH ₂ ) _p COOR is bonded. It is preferable at the point which can make hygroscopicity of resin low.

(Copolymerizable monomer)
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene.

The number of carbon atoms in the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

(Ring-opening polymerization catalyst)
As the catalyst for ring-opening (co) polymerization used in the present invention, a catalyst described in Olefin Metathesis and Metathesis Polymerization (K.J.IVIN, J.C.MOL, 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) Li, Na, K, Mg, Ca, Zn, Cd, Hg. A metathesis polymerization catalyst comprising a combination of at least one selected from the group consisting of at least one element-carbon bond or the element-hydrogen bond, such as B, Al, Si, Sn, Pb, etc. Can be mentioned. This catalyst may be added with an additive (c) described later in order to increase the activity of the catalyst. Examples of the other catalyst include (d) a metathesis catalyst composed of Group 4 to Group 8 transition metal-carbene complex, metallacyclobutane complex, or the like that does not use a promoter.

Representative examples of W, Mo, Re, V and Ti compounds suitable as the component (a) include WCl ₆ , MoCl ₅ , ReOCl ₃ , VOCl ₃ , TiCl _{4 and the} like.
And the compounds described in No. 7 publication.

As the component (b), n-C ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl,
Examples thereof include (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like described in JP-A-1-240517.

  As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably used, and further compounds described in JP-A-1-240517 should be used. Can do.

Representative examples of the catalyst (d), W (= N -2,6-C 6 H 3 iPr 2) (= CH tBu) (
_{O tBu) 2, Mo (=} N-2,6-C 6 H 3 iPr 2) (= CH tBu) (O tBu) 2, Ru (= CHCH = CPh 2) (PPh 3) 2 Cl 2, Ru ( = CHPh) (PC ₆ H ₁₁ ) ₂ Cl _{2 and the} like.

The amount of the metathesis catalyst used is the moles of the component (a) and all monomers (norbornene monomers (Im), (IIm) and other copolymerizable monomers; the same applies hereinafter). The ratio of “(a) component: all monomers” is usually in the range of 1: 500 to 1: 500,000, preferably 1.
The range of 1,000 to 1: 100,000 is desirable. The ratio of the component (a) to the component (b) is such that the metal atomic ratio “(a) :( b)” is in the range of 1: 1 to 1: 100, preferably 1: 2 to 1:50. Is desirable. Moreover, when adding the said (c) additive to this metathesis catalyst, the ratio of (a) component and (c) component is 0.005: 1 to ((c) :( a)) by molar ratio. Desirably, it is in the range of 15: 1, preferably 0.05: 1 to 7: 1. Further, the amount of the catalyst (d) used is usually from 1:50 to 1: 100,000, with “(d) component: total monomer” being the molar ratio of the component (d) to the total monomer. Range, preferably 1: 100 to 1: 5
It is desirable that the range be in the range of 0.00.

(Solvent for polymerization reaction)
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight regulator solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane and decane. ; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene , Compounds such as halogenated alkanes such as chloroform and tetrachloroethylene, and aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane S; dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, it may be mixed singly, or two or more. Of these, aromatic hydrocarbons are preferred.
As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

(Molecular weight regulator)
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.

  Examples of suitable molecular weight regulators include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. And styrene, among which 1-butene and 1-hexene are particularly preferable.

These molecular weight regulators can be used alone or in combination of two or more.
The amount of the molecular weight regulator used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

  (II) In order to obtain a ring-opening copolymer, in the ring-opening polymerization step, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization. Furthermore, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.

The ring-opening (co) polymer obtained as described above can be used as it is, but the (III) hydrogenated (co) polymer obtained by further hydrogenation is a resin having high impact resistance. It is useful as a raw material.

(Hydrogenation catalyst)
As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Any known heterogeneous catalyst and homogeneous catalyst can be used as the hydrogenation catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania.

Homogeneous catalysts include nickel naphthenate / triethylaluminum, bis (acetylacetonato) nickel (II) / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (tritri Phenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, (acetoxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium, And (4-pentylbenzoyloxy) carbonyl (hydrido) bis (triphenylphosphine) ruthenium.

The form of the catalyst may be powder or granular. Further, the hydrogenation reaction catalyst can be used alone or in combination of two or more.
Although it is necessary to adjust the amount of these hydrogenation catalysts appropriately, usually, the “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” is 1: 1 × 10 ⁻⁶ to It is desirable to use at a ratio of 1: 2.

(Cyclization by Friedel-Craft reaction)
The method for cyclizing the ring-opened (co) polymer of (I) or (II) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. Any known method can be employed. Specifically, Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₂ ClCOOH, zeolite, activated clay, and Bronsted acid are used as the acidic compound.

The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the ring-opening (co) polymer of (I) or (II).
Furthermore, as the cyclic polyolefin resin (A), (V) a saturated copolymer of the specific monomer and an unsaturated double bond-containing compound can also be used.

(Unsaturated double bond-containing compound)
Examples of the unsaturated double bond-containing compound include olefinic compounds having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, such as ethylene, propylene, and butene.

The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.
In the present invention, in order to obtain a saturated copolymer of (V) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.

(Addition polymerization catalyst)
As a catalyst for synthesizing the (V) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a co-catalyst are used.

  Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Further, as the vanadium compound, the formula:
VO (OR) _a X _b or V (OR) _c X _d
(Wherein R represents a hydrocarbon group, X represents a halogen atom, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d) ≦ 4, 3 ≦ (c + d) ≦ 4)
Or an electron-donating adduct of these compounds.

  Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes; ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

  Furthermore, as the organoaluminum compound as a cocatalyst, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

  In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 It is in the range of ~ 20.

As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Further, the molecular weight of the obtained (V) saturated copolymer is usually adjusted using hydrogen.

  Furthermore, as the cyclic olefin resin of the present invention, (VI) an addition type of one or more monomers selected from the above-mentioned specific monomer and a vinyl cyclic hydrocarbon monomer or a cyclopentadiene monomer Copolymers and their hydrogenated copolymers can also be used.

(Vinyl cyclic hydrocarbon monomer)
Examples of vinyl cyclic hydrocarbon monomers include vinylcyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene; 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers; 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene; vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane; styrene, α-methylstyrene, 2-methylstyrene, 3-methyls Styrene monomers such as len, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene; d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene; vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene; 4-vinylcycloheptane, 4-isopropenylcycloheptane and the like And vinyl cycloheptane monomers.
Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

(Cyclopentadiene monomer)
(VI) Examples of the cyclopentadiene monomer used as the addition copolymer monomer include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5- Examples thereof include methylcyclopentadiene and 5,5-methylcyclopentadiene. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (V) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the unsaturated double bond-containing compound.

The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the above (III) ring-opening (co) polymer. .
Furthermore, as the cyclic olefin resin of the present invention, (VII) an alternating copolymer of the specific monomer and acrylate can also be used.

(Acrylate)
(VII) Examples of the acrylate used in the production of the alternating copolymer of the specific monomer and the acrylate include, for example, a straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate, Branched or cyclic alkyl acrylate; glycidyl acrylate, 2-tetrahydrofurfuryl acrylate, etc., C2-C20 heterocyclic group-containing acrylate; benzyl acrylate, etc., C6-C20 aromatic ring group-containing acrylate; Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as boronyl acrylate and dicyclopentanyl acrylate.

In the present invention, (VII) in order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The body undergoes radical polymerization at a rate of 45 to 55 mol and acrylate at a rate of 55 to 45 mol.

(VII) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.

  The “alternate copolymer” in the present invention is a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure which is a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

(Characteristic)
The preferred molecular weight of the cyclic polyolefin resin (A) used in the present invention is 0.2 to 5 dL / g, more preferably 0.3 to 3 dL / g, and particularly preferably 0.3 to 3 in terms of intrinsic viscosity [η] _inh. The polystyrene-reduced number average molecular weight [Mn] measured by gel permeation chromatography (GPC) after being dissolved in tetrahydrofuran is 8,000 to 100,000, more preferably 10,000 to 80. 1,000, particularly preferably 12,000 to 50,000, and a weight average molecular weight [Mw] of 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 30,000 to 200. One in the range of 1,000 is preferred. Moreover, molecular weight distribution [Mw / Mn] becomes like this. Preferably it is 2.0-4.0, More preferably, it is 2.5-3.7, More preferably, it is 2.8-3.5.

When the intrinsic viscosity [η] _inh , number average molecular weight and weight average molecular weight are in the above ranges, the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic polyolefin resin (A), and the optical film of the present invention As a result, the moldability becomes better.

  The glass transition temperature [Tg] of the cyclic polyolefin resin (A) used in the present invention is usually 100 ° C. or higher, preferably 100 to 350 ° C., more preferably 110 to 250 ° C., and particularly preferably 110 to 200 ° C. It is. When Tg is less than 100 ° C., it is not preferable because it is deformed by use under high temperature conditions or by secondary processing such as coating or printing. On the other hand, if Tg exceeds 350 ° C., the molding process becomes difficult, and it becomes necessary to increase the heating temperature during the molding process, so that there is a high possibility that the resin will deteriorate due to heat.

(Resin component containing cyclic polyolefin resin (A))
In addition to the cyclic polyolefin resin (A), the resin component containing the cyclic polyolefin resin (A) is a range that does not impair the effects of the present invention, preferably 0 to 60% by weight when the resin component is 100% by weight. For example, specific hydrocarbon resins described in JP-A-9-221577 and JP-A-10-287732, or known thermoplastic resins, thermoplastic elastomers, rubbery polymers, organic fine particles, Inorganic fine particles may be blended.

[Compound containing phosphorus atom and halogen atom in the same molecule (B)]
The compound (B) containing a phosphorus atom and a halogen atom in the same molecule used in the present invention is not particularly limited as long as it is a compound containing a phosphorus atom and a halogen atom in the same molecule. The compound represented by 1) is preferable, and the compound (B) having such a structure has high compatibility with the cyclic polyolefin resin and can provide a composition having excellent transparency. Is preferred.

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、酸素原子、リン原子、硫黄原子、窒素
原子またはケイ素原子を含む連結基を有してもよい置換または非置換の炭素数１〜２０の炭化水素基；または極性基を表し、Ｒ¹〜Ｒ³の少なくとも１つは、ハロゲン原子を含む。）
上記式（１）で表される化合物の具体例として、以下の化合物が挙げられるが、本発明はこれらの具体例に限定されるものではない。
トリス（クロロプロピル）ホスフェート、
トリス（ジクロロプロピル）ホスフェート、
トリス（トリクロロネオペンチル）ホスフェート、
トリス（ブロモプロピル）ホスフェート、
トリス（ジブロモプロピル）ホスフェート、
トリス（トリブロモネオペンチル）ホスフェート、
２，２−ビス（クロロメチル）−１，３−プロパンジイルビス[ビス（トリブロモネオペ
ンチル）ホスフェート
などが挙げられる。これらは１種単独で、または２種以上併用することができる。

(Wherein R ¹ , R ² and R ³ each independently represents a substituted or unsubstituted carbon atom which may have a linking group containing an oxygen atom, a phosphorus atom, a sulfur atom, a nitrogen atom or a silicon atom, 1 -20 hydrocarbon group; or a polar group, and at least one of R ^{1 to} R ³ contains a halogen atom.)
Specific examples of the compound represented by the above formula (1) include the following compounds, but the present invention is not limited to these specific examples.
Tris (chloropropyl) phosphate,
Tris (dichloropropyl) phosphate,
Tris (trichloroneopentyl) phosphate,
Tris (bromopropyl) phosphate,
Tris (dibromopropyl) phosphate,
Tris (tribromoneopentyl) phosphate,
Examples include 2,2-bis (chloromethyl) -1,3-propanediylbis [bis (tribromoneopentyl) phosphate. These can be used alone or in combination of two or more.

Among the compounds (B), R ¹ , R ² and R ³ in the formula (1) are preferably 1 to 17 carbon atoms, more preferably 3 to 17 hydrocarbon groups. A phosphorus atom may be contained, and the halogen atom contained is preferably chlorine or bromine.

  Examples of the polar group of the compound (B) include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group, and these polar groups are linked via a linking group such as a methylene group. May be combined. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Of these compounds (B), 2,2-bis (chloromethyl) -1,3-propanediylbis [bis (tribromoneopentyl) phosphate represented by the following formula (B-1), and Tris (tribromoneopentyl) phosphate represented by the formula (B-2) is particularly preferred, and “CR-900” (Daihachi Chemical Industry Co., Ltd.) is a commercially available compound represented by the following formula (B-2). ))) Can be used.

［リン系化合物（Ｃ）］
リン系化合物（Ｃ）としては、樹脂成分の難燃剤として作用し、リン原子を含み、かつ
ハロゲン原子を含まない化合物を、特に制限なく本発明に用いることができるが、下記式（３）で表される化合物であることが好ましい。

[Phosphorus compound (C)]
As the phosphorus compound (C), a compound that acts as a flame retardant for the resin component and contains a phosphorus atom and does not contain a halogen atom can be used in the present invention without any particular limitation. It is preferable that it is a compound represented.

（式（３）中、Ｒ⁸、Ｒ⁹およびＲ¹¹〜Ｒ¹³は、それぞれ独立に、炭素原子数５〜２０のアリール基を表し、Ｒ¹⁰は、炭素原子数６〜２５のアリーレン基を表し、ｎは、１〜３の整数を表す。）

(In the formula (3), R ⁸ , R ⁹ and R ^{11 to} R ¹³ each independently represents an aryl group having 5 to 20 carbon atoms, and R ¹⁰ represents an arylene group having 6 to 25 carbon atoms. And n represents an integer of 1 to 3.)

Among such phosphorus compounds (C), a compound represented by the following formula (C-1) is more preferable, and 1,3-bis [di (2 ′, 6′-dimethylphenyl) phosphoryl] Benzene, also known as resorcinol bis (dixylenyl phosphate), 1,3-bis [di (2 '
, 6′-dibutylphenyl) phosphoryl] benzene and the like are particularly preferred. The compound having such a structure is suitable because it has a high compatibility with the cyclic polyolefin resin (A), and a composition having excellent transparency can be obtained.

（式（Ｃ−１）中、Ａ⁸〜Ａ¹¹は、それぞれ独立に、水素原子または炭素原子数１〜５の
アルキル基を表す。）
また、リン系化合物（Ｃ）としては、下記式（Ｃ−２）で表される１０−（２，５−ジヒドロキシフェニル）−９，１０−ジヒドロ−９−オキサ−１０−ホスファフェナントレン−１０−オキシドなども用いることができる。

(In formula (C-1), A ^{8 to} A ¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
In addition, as the phosphorus compound (C), 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 represented by the following formula (C-2) An oxide can also be used.

［ハロゲン系化合物（Ｄ）］
ハロゲン系化合物（Ｄ）は、樹脂成分の難燃剤として作用し、ハロゲン原子を含み、かつリン原子を含まない化合物を特に制限なく本発明に用いることができるが、下記式（４）で表される化合物であることが好ましい。

[Halogen compound (D)]
The halogen-based compound (D) acts as a flame retardant for the resin component, and a compound containing a halogen atom and not containing a phosphorus atom can be used in the present invention without any particular limitation, and is represented by the following formula (4). It is preferable that it is a compound.

（式（４）中、Ｘは、ハロゲン原子またはハロゲン原子を含む炭素原子数１〜１０の炭化水素基を表し、Ｙは、５〜１２員環を表し、Ｒ¹⁴は、酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有してもよい置換または非置換の炭素原子数１〜２０の炭化水素基；または極性基を表し、ｍは、１〜１０の整数を表し、ｌとｎとの和は、Ｙを表す環を形成する炭素原子数と同数を表し、ｌおよびｎは、それぞれ１以上の整数を表す。）
上記式（４）で表される化合物としては、具体的に以下の化合物が挙げられるが、本発明はこれらに限定されない。

(In the formula (4), X represents a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms including a halogen atom, Y represents a 5- to 12-membered ring, and R ¹⁴ represents an oxygen atom or a sulfur atom. Represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may have a linking group containing a nitrogen atom or a silicon atom; or represents a polar group, m represents an integer of 1 to 10; And n represents the same number as the number of carbon atoms forming the ring representing Y, and l and n each represents an integer of 1 or more.)
Specific examples of the compound represented by the above formula (4) include the following compounds, but the present invention is not limited thereto.

1,1,2,2-tetrabromoethane,
1,2,3,4-tetrabromoethane,
1,2,3-tribromopropane,
Hexabromobenzene,
Decabromodiphenyl oxide,
Bis (pentabromophenyl) ethane,
Bis (pentabromophenyl) methane,
Bis (tetrabromophenyl) ethane,
Bis (tribromophenoxy) ethane,
Tetrabromophenol A,
Tetrabromobisphenol S,
Tetradecabromodiphenoxybenzene,
2,2-bis (4-hydroxy-3,5-dibromophenylpropane),
Pentabromotoluene,
Pentabromodiphenyl oxide,
Hexabromodiphenyl ether,
Octabromophenol ether,
Octabromodiphenyl ether,
Octabromodiphenyl oxide,
Decabromodiphenyl ether,
Hexabromocyclododecane,
Brominated polystyrene,
Polybrominated styrene,
2,4,6-tribromophenol,
TBBA bis (dibromopropyl ether),
TBBA epoxy oligomer,
2,2,4-dibromophenol,
2,6,4-dibromophenol,
TBBA carbonate oligomer,
Triallyl isocyanurate hexabromide,
Examples include 2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine.

  Among these, a TBBA carbonate oligomer represented by the following formula (D-1) (trade name: Fireguard (registered trademark) 7500, manufactured by Teijin Chemicals Ltd.), a bird represented by the following formula (D-2) Allyl isocyanurate hexabromide (trade name: FCP-660CN, manufactured by Suzuhiro Chemical Co., Ltd.), 4,6-tris (2,4,6-tribromophenoxy) represented by the following formula (D-3) -1,3,5-triazine (trade name: Pyroguard SR-245, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is preferred.

（式（Ｄ−１）中、ｎは、１〜１０を表す。）

(In formula (D-1), n represents 1 to 10)

［他の成分］
上記環状ポリオレフィン系樹脂（Ａ）の透明性などの諸特性を損なわない範囲で、必要に応じて本発明の樹脂組成物に他の難燃剤を添加することができる。上記の他の難燃剤としては、例えば、シリコン化合物、難燃触媒、窒素化合物、ホウ素化合物、水酸化アルミニウム、水酸化マグネシウムなどが挙げられる。

[Other ingredients]
Other flame retardants can be added to the resin composition of the present invention as necessary within a range that does not impair various properties such as transparency of the cyclic polyolefin resin (A). Examples of the other flame retardant include silicon compounds, flame retardant catalysts, nitrogen compounds, boron compounds, aluminum hydroxide, and magnesium hydroxide.

  By adding 0.01 to 5 parts by weight of an antioxidant such as phenol, lactone, phosphorus or thioether to 100 parts by weight of the resin component, the heat deterioration resistance can be further improved. .

Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 4,4′-thiobis- (6-tert-butyl-3-methyl-phenyl), 1,1-bis. (4-hydroxyphenyl) cyclohexane, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), tetrakis [methylene-3-3,5-di-tert-butyl-4-hydroxyphenyl] propionate] methane 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid stearate, 2,5-di-t-butylhydroquinone, pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl)] propionate and the like, hydroquinone antioxidants, bis- (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), tetrakis (2,4-di-t-butyl-5-methylphenyl) ) 4,4′-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite , Phosphorus secondary antioxidants such as tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, dilauryl-3,3′-thiodipropionate, 2-mercaptobenzimidazole And sulfur-based secondary antioxidants such as

Further, for the cyclic polyolefin resin, in the range not impairing the object of the present invention, for example, ultraviolet absorbers such as resorcinol, benzotriazole, benzophenone, lubricants, mold release materials, antistatic agents, fluorescent whitening agents, dyes One or more usual additives such as pigments can be added.

[Method for Producing Resin Composition]
(Resin component (i) + Flame retardant (ii-1))
The content of the resin component (i) including the cyclic polyolefin resin (A) contained in the resin composition of the present invention is 60 to 99 parts by weight, preferably 65 to 98 parts by weight, more preferably 70 to 96 parts by weight. The content of the flame retardant (ii-1) which is a compound (B) containing a phosphorus atom and a halogen atom in the same molecule is 1 to 40 parts by weight, preferably 2 to 35 parts by weight, more preferably Is 4-30 parts by weight.

However, the total of the resin component (i) and the flame retardant (ii-1) is 100 parts by weight.
It is preferable for the content of the resin component (i) and the flame retardant (ii-1) to be in the above range since both heat resistance and flame retardancy can be achieved.

(Resin component (i) + Flame retardant (ii-2))
When the components contained in the resin composition of the present invention are the resin component (i) and the flame retardant (ii-2), that is, the resin component (i), the phosphorus compound (C), and the halogen compound (D). When the total of the compound (C) and the compound (D) is 100% by weight, the content of the compound (C) is preferably 5 to 50% by weight, more preferably 7 to 48% by weight. The content of the compound (D) is preferably 50 to 95% by weight, more preferably 52 to 93% by weight, and particularly preferably 55 to 90% by weight.

When the content ratio of the compound (C) and the compound (D) is within the above range, it is preferable because the self-extinguishing property is high.
In addition, each preferable content of the resin component (i) and the flame retardant (ii-2) and the reason thereof are the same as those described above (resin component (i) + flame retardant (ii-1)). .

(Resin component (i) + Flame retardant (ii-3))
When the components contained in the resin composition of the present invention are the resin component (i) and the flame retardant (ii-3), that is, the resin component (i), the compound (B), and the compound (C). When the total of the compound (B) and the compound (C) is 100% by weight, the content of the compound (B) is preferably 60 to 98% by weight, more preferably 62 to 95% by weight, and particularly preferably The content of compound (C) is preferably 2 to 40% by weight, more preferably 5 to 38% by weight, and particularly preferably 7 to 35% by weight.

When the content ratio of the compound (B) and the compound (C) is within the above range, it is preferable because the transparency is improved.
In addition, the preferable content of the resin component (i) and the flame retardant (ii-3) and the reason thereof are the same as those described above (resin component (i) + flame retardant (ii-1)).

(Resin component (i) + Flame retardant (ii-4))
When the components contained in the resin composition of the present invention are the resin component (i) and the flame retardant (ii-4), that is, the resin component (i), the compound (B), and the compound (D). When the total of the compound (B) and the compound (D) is 100% by weight, the content of the compound (B) is preferably 15 to 60% by weight, more preferably 17 to 58% by weight, and particularly preferably The content of compound (D) is preferably 40 to 85% by weight, more preferably 42 to 83% by weight, and particularly preferably 45 to 80% by weight.

When the content ratio of the compound (B) and the compound (D) is within the above range, it is preferable because the self-extinguishing property is high.
In addition, preferable content of the resin component (i) and the flame retardant (ii-4) and the reason thereof are the same as those described above (resin component (i) + flame retardant (ii-1)).

(Resin component (i) + Flame retardant (ii-5))
When the components contained in the resin composition of the present invention are the resin component (i) and the flame retardant (ii-5), that is, the resin component (i), the compound (B), the compound (C), and the compound (D ), When the total of the compound (B), the compound (C) and the compound (D) is 100% by weight, the content of the compound (B) is preferably 10 to 50% by weight, more preferably Is 20 to 50% by weight, the content of compound (C) is preferably 5 to 45% by weight, more preferably 10 to 40% by weight, and the content of compound (D) is preferably 5 to 45% by weight. 45% by weight, more preferably 10 to 40% by weight.

When the content of the compound (B), the compound (C), and the compound (D) is within the above range, it is preferable because self-digestibility and transparency are improved.
In addition, the preferable content of the resin component (i) and the flame retardant (ii-5) and the reason thereof are the same as those described above (resin component (i) + flame retardant (ii-1)).

By such content (parts by weight), it is usually −5 to 150 ° C., preferably 0 to 30 ° C., and preferably dissolved in a solvent (preferably dichloromethane, toluene, cyclohexane), preferably 3% by weight or more, more preferably Can prepare a uniform and transparent solution having a concentration of 5% by weight or more.
Moreover, when preparing without using a solvent, it is preferable to melt-knead and pelletize each component.

[Characteristics of resin composition]
The glass transition temperature [Tg] of the resin composition is preferably 80 ° C. or higher, more preferably 90 to 250 ° C., and particularly preferably 100 to 200 ° C. If Tg is too low, the heat distortion temperature becomes low, which may cause a problem in heat resistance, and there may be a problem that the change in optical characteristics due to the temperature of the obtained molded product or film becomes large. On the other hand, if Tg is too high, it is necessary to increase the processing temperature, which may cause thermal degradation of the resin composition.

<Molded body>
The molded body formed from the resin composition of the present invention is used as various materials and is suitable for optical parts such as a light guide plate, a retardation film, and a transparent electrode substrate.
The shape of the optical component is not particularly limited, and examples thereof include a film shape, a sheet shape, a lens shape, a thin film shape, and a laminate shape. Of these shapes, a film shape, a sheet shape, or a lens shape is preferable.

[Molding method]
The method for molding the resin composition is not particularly limited, and a solution casting method (casting method), an extrusion molding method, a compression molding method, an injection molding method, and the like can be used. In the solution casting method, a resin composition is dissolved in a solvent to prepare a solution of the composition, and then the solution is applied to a support, and then the solvent is dried to form a film or a sheet. It is a method of obtaining the molded object.
As a method for forming a film or sheet using the resin composition of the present invention, a cast molding method is preferable when the resin composition is a solution, and a melt extrusion molding method is preferable when the resin composition is a pellet.

(Characteristic)
The molded product of the present invention (for example, melt-extruded film, stretched film, etc.) obtained as described above is in accordance with UL94 combustion test (20 mm vertical combustion test (IEC60695-11-10B method; ASTM D3801)). When flammability is evaluated using a CUL combustion test chamber (manufactured by Toyo Seiki Seisakusho Co., Ltd.), self-extinguishment within 10 seconds with one ignition, the absorbent cotton underneath ignites, and the amount of drip It is preferable that self-extinguish and absorbent cotton ignite within 5 seconds after one ignition, but it is more preferable that the amount of drip is small, and self-extinguish and absorbent cotton ignite within 5 seconds after one ignition. It is particularly preferred that the amount of drip is small. The test piece was pelletized with a resin composition using a twin screw extruder (trade name: TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), and an injection molding machine (trade name: SG75MS, manufactured by Sumitomo Heavy Industries). Then, injection molding is performed under the conditions of a resin temperature of 260 to 300 ° C. and a mold temperature of 80 to 140 ° C., and a flat plate of 125 × 13 mm and a thickness of 2 mm is used.

  Further, the molded article of the present invention is preferably a film having a film thickness of about 100 μm by cast molding, when haze is measured using a haze meter (HM-150 type, manufactured by Murakami Color Research Laboratory Co., Ltd.). It is less than 1.0%. If the haze of the molded product is within the above range, the transparency is not impaired, which is preferable.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.

In the following examples and comparative examples, the measurement and evaluation of each physical property value were in accordance with the following (1) to (3).
First, using the resin composition of the present invention, a test piece made of a film or a molded plate was produced as follows.

(Production of test piece made of film)
A 5% methylene chloride solution of the prepared resin composition was cast to produce a film. Specifically, the solution is poured on a clean A4 glass plate, covered, left to stand at room temperature for 24 hours, and vacuum-dried at 100 ° C. for 24 hours after peeling to obtain a film having a thickness of about 100 μm. Produced.
The obtained film was cut into 200 mm × 50 mm to obtain a test piece.

(Production of test piece made of molded plate)
The prepared resin composition was pelletized by a twin-screw extruder (trade name: TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), which was then injection molded (trade name: SG75MS, Sumitomo Heavy Industries, Ltd.). And injection molding under the conditions of a resin temperature of 260 to 300 ° C. and a mold temperature of 80 to 140 ° C., and a flat plate of 125 mm × 12.5 mm and a thickness of 2 mm was molded to obtain a test piece.

(1) Glass transition temperature [Tg]
A differential scanning calorimeter (trade name: DSC6200, Seiko Instruments Inc.) was used for the extrapolated glass transition start temperature (° C.) of the resin composition in accordance with the Japanese Industrial Standard (JIS) K7121. )).

(2) Combustion test According to UL94 combustion test (20 mm vertical combustion test (IEC60695-11-10B method; ASTM D3801)), flammability was measured using an HVUL-C UL combustion test chamber (manufactured by Toyo Seiki Seisakusho Co., Ltd.). Evaluation was performed.
The evaluation of the flammability was carried out in three stages with respect to the drip at the time of the combustion test of the test piece consisting of a film and a molded plate.
A: Self-extinguish within 5 seconds with one ignition of the test piece. And the amount of drip is small, and the absorbent cotton laid under the test piece does not ignite.
○: Self-extinguish within 5 seconds with one ignition on the specimen. And the absorbent cotton laid under the test piece ignites, but the amount of drip is small.
X: Self-extinguish within 10 seconds by one ignition to the test piece. And the absorbent cotton laid under the test piece ignites and the amount of drip is large.

(3) Transparency evaluation The test piece which consists of a film was further prepared so that it might become width: 10mm and length: 90mm, haze (%) was measured, and 2 steps | paragraphs evaluated.
○: Haze is less than 1.0%.
X: Haze is 1.0% or more.
For the measurement of haze, a haze meter (HM-150 type, manufactured by Murakami Color Research Laboratory Co., Ltd.) was used.

[Synthesis Example 1]
8-methoxycarbonyl-8-methyltetracyclo represented by the following formula [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (100 g), 1-hexene (3.6 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 methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added and reacted at 80 ° C. for 1 hour to open the ring. A polymer was obtained.

次いで、得られた開環重合体溶液に水素添加反応触媒であるＲｕＨＣｌ（ＣＯ）［Ｐ（Ｃ₆Ｈ₅）₃］₃を０．０４ｇ添加し、水素ガス圧を９〜１０ＭＰａとし、１６０〜１６５℃の温度で、３時間反応させた。反応終了後、得られた生成物を多量のメタノール中で沈殿させることにより水素添加物を得た。

Subsequently, 0.04 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation reaction catalyst was added to the obtained ring-opening polymer solution, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and 160 to The reaction was carried out at a temperature of 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.

The obtained polymer had a glass transition temperature [Tg] of 167 ° C. and an intrinsic viscosity [η] _inh of 0.79.
dL / g, polystyrene-reduced number average molecular weight [Mn] measured by gel permeation chromatography (GPC) dissolved in tetrahydrofuran is 28,800, weight average molecular weight [Mw] is 144,000, molecular weight distribution [Mw / Mn] was 5.0, and the yield was 90 g (yield 90%). Moreover, the hydrogenation rate of this hydrogenated substance calculated | required by 500 MHz and < ¹ > H-NMR measurement was 99.0% or more. The hydrogenated product of the obtained ring-opening polymer is referred to as “A-1”.

[Example 1]
As resin component (i), 95 parts of A-1 obtained in Synthesis Example 1 and as compound (B), tris (tribromoneopentyl) phosphate represented by the following formula (B-1) (trade name) : CR-900, manufactured by Daihachi Chemical Industry Co., Ltd.) was dissolved in dichloromethane at room temperature to obtain a uniform and transparent 5% solution. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

［実施例２］
実施例１において、樹脂成分（ｉ）を７８．１部、化合物（Ｂ）を０部、化合物（Ｃ）として下記式（Ｃ−１）で表される非ハロゲン縮合リン酸エステル（商品名：ＰＸ−２００、大八化学工業（株）製）を４．４部、および化合物（Ｄ）として下記式（Ｄ−１）で表されるＴＢＢＡカーボネートオリゴマー（商品名：ファイヤガード７５００、帝人化成（株）製）１７．５部を用いた以外は実施例１と同様にして５％溶液を調製した。上記（１）〜（３）に係る各物性値および評価結果を表１に示す。

[Example 2]
In Example 1, 78.1 parts of resin component (i), 0 part of compound (B) and non-halogen condensed phosphate represented by the following formula (C-1) (trade name: Compound (C)) 4.4 parts of PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), and TBBA carbonate oligomer represented by the following formula (D-1) as a compound (D) (trade name: Fireguard 7500, Teijin Chemicals ( A 5% solution was prepared in the same manner as in Example 1 except that 17.5 parts) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

（式（Ｄ−１）中、ｎは、１〜１０を表す。）

(In formula (D-1), n represents 1 to 10)

[Example 3]
In Example 2, 81.7 parts of resin component (i) and triallyl isocyanurate hexabromide represented by the following formula (D-2) as compound (D) (trade name: FCP-660CN, Suzuhiro Chemical) A 5% solution was prepared in the same manner as in Example 2 except that 13.9 parts were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

［実施例４］
実施例２において、樹脂成分（ｉ）を８２．０部、および化合物（Ｄ）として下記式（Ｄ−３）で表される４，６−トリス（２，４，６−トリブロモフェノキシ）−１，３，５−トリアジン（商品名：ピロガードＳＲ−２４５、第一工業製薬（株）製）１３．６部を用いた以外は実施例２と同様にして５％溶液を調製した。また、同様の組成で射出成形により成形板を得た。上記（１）〜（３）に係る各物性値および評価結果を表１に示す。

[Example 4]
In Example 2, 82.0 parts of the resin component (i) and 4,6-tris (2,4,6-tribromophenoxy)-represented by the following formula (D-3) as the compound (D) A 5% solution was prepared in the same manner as in Example 2 except that 13.6 parts of 1,3,5-triazine (trade name: Pyroguard SR-245, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. Further, a molded plate was obtained by injection molding with the same composition. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

［比較例１］
実施例１において、樹脂成分（ｉ）を１００部、および化合物（Ｂ）を０部とした以外は実施例１と同様にして５％溶液を調製した。上記（１）〜（３）に係る各物性値および評価結果を表１に示す。

[Comparative Example 1]
A 5% solution was prepared in the same manner as in Example 1 except that 100 parts of the resin component (i) and 0 parts of the compound (B) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 2]
A 5% solution was prepared in the same manner as in Example 2 except that 95.6 parts of the resin component (i) and 0 parts of the compound (D) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 3]
In Comparative Example 2, a 5% solution was prepared in the same manner as in Comparative Example 2, except that 90 parts of the resin component (i) and 10 parts of the compound (C) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 4]
A 5% solution was prepared in the same manner as in Example 2 except that 82.5 parts of the resin component (i) and 0 parts of the compound (C) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 5]
In Comparative Example 4, a 5% solution was prepared in the same manner as in Comparative Example 4 except that 70 parts of the resin component (i) and 30 parts of the compound (D) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 6]
In Example 3, a 5% solution was prepared in the same manner as in Example 3 except that 86.1 parts of the resin component (i) and 0 parts of the compound (C) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 7]
In Comparative Example 6, a 5% solution was prepared in the same manner as in Comparative Example 6 except that 80 parts of the resin component (i) and 20 parts of the compound (D) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 8]
A 5% solution was prepared in the same manner as in Example 4 except that the resin component (i) was 84.4 parts and the compound (C) was 0 parts in Example 4. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

[Comparative Example 9]
In Comparative Example 8, a 5% solution was prepared in the same manner as in Comparative Example 8, except that 80 parts of the resin component (i) and 20 parts of the compound (D) were used. Table 1 shows the physical property values and evaluation results according to the above (1) to (3).

  The molded body formed by molding the resin composition of the present invention utilizes the excellent transparency, heat resistance, mechanical properties, and flame retardancy, and sealing materials and protective films for electrical and electronic parts including optical parts It is suitable as a material or an insulating material.

  The “optical component” can be suitably used as an optical lens, a film, or a sheet. Specific examples thereof include a light guide plate, a retardation film, a protective film, an adhesive film, a touch panel, a transparent electrode substrate, a TFT substrate, Examples include color filter substrates.

Examples of the “sealing material / protective film material for electrical / electronic components” include, for example, copper-clad laminates for printed wiring boards, interlayer insulation films for build-up multilayer wiring layers for high-density mounting boards, and insulation materials for semiconductor package boards Examples thereof include encapsulants for transfer molding materials for semiconductor parts, encapsulants for underfill, buffer coat films, passivation films, protective films for solder resists, and the like.
Examples of the “insulating material” include coating materials such as electric wires and cables; insulating materials for OA equipment such as computers, printers, and copiers.

Claims (10)

(I) 60 to 99 parts by weight of a resin component containing the cyclic polyolefin resin (A);
(Ii) 1 to 40 parts by weight of a flame retardant (however, the total of the following (i) and the following (ii) is 100 parts by weight)
Including
The flame retardant (ii) is
(Ii-1) Compound (B) containing a phosphorus atom and a halogen atom in the same molecule,
(Ii-2) phosphorus compound (C) and halogen compound (D),
(Ii-3) The compound (B) and the compound (C),
(Ii-4) The compound (B) and the compound (D), or (ii-5) The compound (B), the compound (C) and the compound (D)
The resin composition characterized by including. The flame retardant (ii-2) is
5 to 50% by weight of the phosphorus compound (C) and 50 to 95% by weight of the halogen compound (D)
(However, the total of the compound (C) and the compound (D) is 100% by weight)
The resin composition according to claim 1, comprising:   Glass transition temperature [Tg] is 80 degreeC or more, The resin composition of Claim 1 or 2 characterized by the above-mentioned. The said compound (B) is a compound represented by following formula (1), The resin composition in any one of Claims 1-3 characterized by the above-mentioned.

(Wherein R ¹ , R ² and R ³ are each independently substituted or unsubstituted carbon atoms which may have a linking group containing an oxygen atom, a phosphorus atom, a sulfur atom, a nitrogen atom or a silicon atom) 1 to 20 hydrocarbon groups; or a polar group, and at least one of R ^{1 to} R ³ contains a halogen atom.) The resin according to any one of claims 1 to 4, wherein the resin (A) is a (co) polymer having a structural unit derived from a monomer represented by the following formula (2). Composition.

(In the formula (2), R ^{4 to} R ⁷ each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms or other monovalent organic group, and R ^{4 to} R ⁷ Any two of them may be bonded to each other to form a monocycle or polycycle, and m and n each independently represents 0 or a positive integer.) The resin composition according to any one of claims 1 to 5, wherein the phosphorus compound (C) is a compound represented by the following formula (3).

(In the formula (3), R ⁸ , R ⁹ and R ^{11 to} R ¹³ each independently represents an aryl group having 5 to 20 carbon atoms, and R ¹⁰ represents an arylene group having 6 to 25 carbon atoms. And n represents an integer of 1 to 3.) The said halogen-type compound (D) is a compound represented by following formula (4), The resin composition in any one of Claims 1-6 characterized by the above-mentioned.

(In the formula (4), X represents a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms including a halogen atom, Y represents a 5- to 12-membered ring, and R ¹⁴ represents an oxygen atom or a sulfur atom. A substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms which may have a linking group containing a nitrogen atom or a silicon atom; or a polar group, m represents an integer of 1 to 10; And n represents the same number as the number of carbon atoms forming the ring representing Y, and l and n each represents an integer of 1 or more.)   A molded article formed using the resin composition according to claim 1.   The molded article according to claim 8, wherein the molded article is for an optical component.   The molded article according to claim 9, wherein the shape of the optical component is a film shape, a sheet shape, or a lens shape.