JP2010248339A - Resin composition and molded product thereof - 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 olefin resin, and also exhibits excellent flame retardancy when molded. <P>SOLUTION: The resin composition includes: 75-99 pts.wt. of cyclic olefin resin (A); and 1-25 pts.wt. of a compound (B) containing a phosphorus atom and a nitrogen atom and expressed by formula (1) (wherein R<SP>1</SP>is independently a 1-10C hydrocarbon group which may have a substituent, a 3-10C alicyclic hydrocarbon group which may have a substituent or a 6-20C aromatic hydrocarbon group which may have a substituent). In the resin composition, the total content of the phosphorus atom and the nitrogen atom is 0.1-5 wt.%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition containing a cyclic olefin resin. More specifically, the present invention relates to a resin composition containing a cyclic olefin resin and a specific flame retardant, and a molded article formed 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, due to increased concern about environmental problems and safety to the human body, there has also been a problem that the use of halogen-based and antimony-based flame retardants that generate harmful gases during the combustion of the resin composition is not preferred.

  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, it has been difficult to obtain good flame retardancy while maintaining the preferable transparency, heat resistance and mechanical properties inherent in the cyclic olefin ring-opening polymer. In addition, there was room for improvement in flame retardancy. Furthermore, in consideration of the safety to the environment and the human body, it has been desired to suppress the phosphorus content in the resin composition as much as possible.

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 that maintains the preferable transparency, heat resistance, and mechanical properties inherently possessed by a cyclic olefin-based resin when molded, is excellent in flame retardancy, and is friendly to the environment and the human body. And

  As a result of earnest research to solve the above-mentioned problems, the present inventors have obtained a specific cyclic olefin resin and a compound having a phosphorus atom and a nitrogen atom in the same molecule at a specific ratio, so that the transparent The present inventors have found that a cyclic olefin-based resin composition having excellent heat resistance, heat resistance and mechanical properties, excellent flame retardancy, and environment and human body can be obtained, and the present invention has been completed.

That is, the resin composition of the present invention is
It contains 75 to 99 parts by weight of the cyclic olefin resin (A) and 1 to 25 parts by weight of the compound (B) containing a phosphorus atom and a nitrogen atom represented by the following formula (1) (however, the component (A) and the component The total content of (B) is 100 parts by weight), and the total content of phosphorus atoms and nitrogen atoms in the resin composition is 0.1 to 5% by weight (however, the total resin composition is 100%). The resin composition is characterized in that the weight percentage is set to be% by weight.

[In formula (1), each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent,
An alicyclic hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. ]
When the solid content contained in the resin composition is 100% by weight, the content of the compound (B) is preferably less than 25% by weight.
The glass transition temperature [Tg] is preferably 100 ° C. or higher.

  The cyclic olefin resin (A) preferably has a structural unit derived from a monomer represented by the following formula (2).

(In Formula (2), R < ² > -R < ⁵ > represents a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group each independently, R < ² > -R < ⁵ > 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 compound (B) is preferably a compound represented by the following formula (3).

[In Formula (3), each R ⁶ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alicyclic carbon atom having 3 to 10 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydrogen group or a substituent. q represents an integer of 0 to 5. ]
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.

  Furthermore, since the phosphorus content and the nitrogen content are suppressed, adverse effects on the environment and the human body after disposal are suppressed, and the balance between safety and the environment is high and suitable.

  Next, the present invention will be specifically described.

<Resin composition>
The resin composition of the present invention contains the cyclic olefin resin (A) and the compound (B) as essential components.

[Cyclic olefin resin (A)]
The cyclic olefin 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 following (co) polymers may be mentioned as such (co) polymers.

(In Formula (2), R < ² > -R < ⁵ > represents a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group each independently, R < ² > -R < ⁵ > 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 (co) polymers of specific monomers with one or more monomers selected from vinyl-based cyclic hydrocarbon monomers and cyclopentadiene monomers and their hydrogenation (co-) Polymer.
(VII) An alternating copolymer of a specific monomer and an acrylate.

Of these, the hydrogenated (co) polymers of the polymers (III) to (IV) and (VI) and the saturated copolymer (V), which are excellent in both optical properties and processing properties, are preferred, particularly (III A hydrogenated (co) polymer of a ring-opening (co) polymer of (1) is 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 ^7,1 ] -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 ² and R ⁴ 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. R ³ and R ⁵ are a hydrogen atom or a monovalent organic group. It is desirable that at least one of R ³ and R ⁵ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group. m and n are each independently preferably 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 cyclic olefin resin obtained 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 ³ and R ⁵ is a polar group represented by the formula: — (CH ₂ ) _p COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, low hygroscopicity, It is preferable at the point which has the outstanding adhesiveness with material. In the formula relating to the specific polar group, R is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms, 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 ² or R ⁴ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably an alkyl group having 1 to 2 carbon atoms, particularly a methyl group. In particular, it is obtained that this alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula: — (CH ₂ ) _p COOR is bonded. This is preferable in that the hygroscopicity of the cyclic olefin resin can be lowered.

(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 a catalyst for ring-opening (co) polymerization used in ring-opening (co) polymerization of a specific monomer or ring-opening (co) polymerization of a specific monomer and a copolymerizable monomer in the present invention, Olefin The catalysts described in Metathesis and Metathesis Polymerization (KJ IVIN, JC MOL, Academic Press 1997) are 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 molar ratio of the above component (a) to the total monomers (specific monomers and other copolymerizable monomers; hereinafter the same) “component (a): The range of “total monomer” is usually from 1: 500 to 1: 500,000, preferably from 1: 1,000 to 1: 100,00.
A range of 0 is desirable. The ratio of the component (a) to the component (b) is, in terms of metal atomic ratio, “(a) :( b)” is usually 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. It is desirable that the range be within a range, preferably 1: 100 to 1: 50,000.

(Solvent for polymerization reaction)
Examples of the solvent used in the ring-opening polymerization reaction (the solvent constituting the molecular weight regulator solution described later, the solvent for the specific monomer and / or the metathesis catalyst) include, for example, pentane, hexane, heptane, octane, nonane and decane. Alkanes; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide Compounds such as halogenated alkanes such as chlorobenzene, chloroform and tetrachloroethylene, aryl halides; saturated carboxylic acids such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane Ester ethers; dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they 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. It is desirable 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 or 1-hexene is particularly preferred.

  These molecular weight regulators can be used alone or in combination of two or more.

  As the usage-amount of a molecular weight regulator, it is 0.005-0.6 mol normally with respect to 1 mol of specific monomers with which it uses for ring-opening polymerization reaction, Preferably it uses 0.02-0.5 mol.

  (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. Presence of unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain such as conjugated diene polymers, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, and polynorbornene. The specific monomer may be subjected to ring-opening polymerization below.

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. In addition, this hydrogenation reaction catalyst can be used alone or in combination with 2
It can also be used by combining more than one species.

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 olefin resin (A), (V) a saturated copolymer of the specific monomer and the 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 ⁷ ) _a X _b , or V (OR ⁷ ) _c X _d
(Wherein R ⁷ 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.

  As the electron donor in the above electron donating adduct, 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, etc. Nitrogen-containing electron donors such as ammonia, amine, nitrile, isocyanate and the like.

  Furthermore, as the organoaluminum compound as the promoter, 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 usually 2 or more, preferably 2 to 50, particularly preferably. It is in the range of 3-20.

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.

  Further, as the cyclic olefin resin of the present invention, (VI) an addition type of the above specific monomer and one or more monomers selected from vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers. 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.
Preferably, it is styrene or α-methylstyrene.
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 the specific monomer and one or more monomers selected from vinyl-based cyclic hydrocarbon monomers and cyclopentadiene monomers is the above-mentioned (V) specific monomer It can be obtained by the same addition polymerization method as the saturated copolymer of the compound and 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 usually 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 olefin-based 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 0.8 in intrinsic viscosity [η] _inh .
The number average molecular weight [Mn] in terms of polystyrene measured by gel permeation chromatography (GPC) after being dissolved in tetrahydrofuran is 8,000 to 100,000, more preferably 10,000. -80,000, particularly preferably 12,000-50,000, and a weight average molecular weight [Mw] of 20,000-300,000, more preferably 30,000-250,000, particularly preferably 30,000. Those in the range of ~ 200,000 are preferred. Moreover, molecular weight distribution [Mw / Mn] becomes like this. Preferably it is 2.0-6.5, More preferably, it is 2.5-6.0, Most preferably, it is 2.8-5.5.

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 olefin 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 olefin 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 a high temperature condition 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. Therefore, the possibility that the resin is deteriorated by heat increases.

(Resin component containing cyclic olefin resin (A))
In addition to the cyclic olefin resin (A), the resin component containing the cyclic olefin resin (A) is within a range not impairing 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 represented by the following formula (1) (B)]
The compound (B) represented by the following formula (1) used in the present invention contains a phosphorus atom and a nitrogen atom in the same molecule and is used as a flame retardant.

  The compound (B) having such a structure is suitable because it has a high compatibility with the cyclic olefin resin and a composition having excellent transparency can be obtained.

[In Formula (1), each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alicyclic carbon atom having 3 to 10 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydrogen group or a substituent. ]
Specific examples of the compound represented by the formula (1) include compounds represented by the following formula (3), but the present invention is not limited to these specific examples.

[In Formula (3), each R ⁶ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alicyclic carbon atom having 3 to 10 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydrogen group or a substituent. q represents an integer of 0 to 5. ]
A compound (B) can be used individually by 1 type or in combination of 2 or more types.

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

  Further, 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 cyclic olefin resin component, the heat deterioration resistance is further improved. It can be 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

Furthermore, for the cyclic olefin-based resin, as long as the object of the present invention is not impaired,
One or more usual additives such as ultraviolet absorbers such as resorcinol, benzotriazole and benzophenone, lubricants, mold release materials, antistatic agents, fluorescent brighteners, dyes and pigments can be added.

[Method for Producing Resin Composition]
The content of the cyclic olefin resin (A) contained in the resin composition of the present invention is 75 to 99 parts by weight, preferably 77 to 98 parts by weight, more preferably 80 to 97 parts by weight. The content of the compound (B) containing a phosphorus atom and a nitrogen atom in the same molecule represented by 1) is 1 to 25 parts by weight, preferably 2 to 23 parts by weight, more preferably 3 to 20 parts by weight. . However, the total of the cyclic olefin resin (A) and the compound (B) containing a phosphorus atom and a nitrogen atom in the same molecule represented by the above formula (1) is 100 parts by weight.

<Content of phosphorus atom and nitrogen atom>
The resin composition of the present invention has a total content of phosphorus atoms and nitrogen atoms of 0.1 to 5% by weight, preferably 0.1 to 3% by weight, more preferably 0.5 to 3% by weight. (However, the entire resin composition is 100% by weight).
When the total content of phosphorus atoms and nitrogen atoms is in the above range, char is generated during combustion, and at the same time, the non-flammable nitrogen gas is generated in a good balance, so that the flame retardant effect is enhanced.
The phosphorus atom and nitrogen atom contents in the resin composition of the present invention were measured by the same method as in the examples.

<Content of Compound (B) in Solid Content>
In the resin composition of the present invention, the content of the compound (B) in the total solid content contained in the resin composition is preferably less than 25 wt%, more preferably 1 to 20 wt%, most preferably 1 ~ 15% by weight. However, the total solid content in the resin composition is 100% by weight. Solid content is a substance that is solid at room temperature.

In the resin composition of the present invention, the cyclic olefin-based resin (A), the compound (B), and other components as necessary in the above content (parts by weight) are usually −5 to 150 ° C., preferably 0 to 30. By dissolving in a solvent (preferably dichloromethane, toluene, cyclohexane) at 0 ° C., a uniform and transparent solution having a concentration of preferably 3% by weight or more, more preferably 5% by weight or more can be prepared.
Moreover, when preparing without using a solvent, it is preferable to melt-knead and pelletize each component.

[Characteristics of resin composition]
As glass transition temperature [Tg] of the resin composition of this invention, 100 degreeC or more is preferable, 105-200 degreeC is more preferable, and 110-180 degreeC is especially preferable. If Tg is lower than the above range, 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 properties due to the temperature of the obtained molded product or film becomes large. is there. On the other hand, when Tg is higher than the above range, it is necessary to increase the processing temperature, and the resin composition may be thermally deteriorated.

<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, extruded film, stretched film, etc.) obtained as described above is HVUL-C according to UL94 combustion test (20 mm vertical combustion test (IEC60695-11-10B method; ASTM D3801)). When evaluation of flammability was performed using a UL combustion test chamber (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the self-extinguishment within 5 seconds after one ignition of the test piece of the test. It is preferable that the absorbent cotton laid down ignites, but the amount of drip is small. It is preferable to meet the criteria of "Self-extinguish within 2 seconds with one ignition of the specimen. And lay under the specimen." It is more preferable that the absorbent cotton ignites, but the amount of drip is small. “The self-extinguishment within one second of the ignition of the test piece within two seconds. It is particularly preferable to apply the standards of the cotton does not fire. ".

  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). And injection molded under conditions of a resin temperature of 260 to 300 ° C. and a mold temperature of 80 to 140 ° C. and molded into a flat plate of 125 × 13 mm and a thickness of 2 mm.

  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 (4).

  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)
Each component shown in Table 1 was dissolved in dichloromethane at room temperature to prepare a 5% dichloromethane solution. The resulting 5% dichloromethane solution 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)
Each component shown in Table 1 is pelletized by a twin screw extruder (trade name: TEM-37BS, manufactured by Toshiba Machine Co., Ltd.), and is then pelletized by an injection molding machine (trade name: SG75MS, Sumitomo Heavy Industries, Ltd.) ), And injection molded 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 formed into a test piece.

(1) Glass transition temperature [Tg]
Using a test piece made of a film, the extrapolated glass transition start temperature (° C.) of the resin composition, that is, the so-called glass transition temperature [Tg] (° C.) is measured according to the Japanese Industrial Standard (JIS) K7121 (differential scanning calorimeter (product). Name: DSC6200, manufactured by Seiko Instruments Inc.)

(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 by four grades for the drip at the time of the combustion test of the test piece composed of the film and the molded plate.
A: Self-extinguishes within 2 seconds by one ignition to the test piece. And the cotton wool laid under the test piece does not ignite.
○: Self-extinguish within 2 seconds with one ignition on the specimen. And the absorbent cotton laid under the test piece ignites, but the amount of drip is small.
Δ: 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 cut so that it might become width: 50mm and length: 90mm, haze (%) was measured, and two steps evaluation was carried out.
○: 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.
(4) Content rate of phosphorus atom and nitrogen atom The intensity | strength of the fluorescent X-ray was measured using the spectris fluorescent X-ray apparatus (model number: Panalical MagicPRO). Using a calibration curve prepared in advance with a sample having a known content, the content was converted to the content of phosphorus atoms and nitrogen atoms in the entire resin composition.

  Table 1 shows the contents of the above (4) phosphorus atoms and nitrogen atoms, and the physical properties and evaluation results according to (1) to (3).

[Synthesis Example 1]
8-methyl-8-methoxycarbonyltetracyclo [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.

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 equivalent number average molecular weight [Mn] measured by gel permeation chromatography (GPC) dissolved in tetrahydrofuran (28800), weight average molecular weight [Mw] 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 (A), 95 parts of A-1 obtained in Synthesis Example 1 and as compound (B), a phosphazene compound represented by the following formula (B-1) (phenoxyphosphazene, trade name: Using 5 parts of SPS-100 (manufactured by Otsuka Chemical Co., Ltd.), a test piece of a film and a molded body was prepared according to the test piece preparation method. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the resin composition obtained above, the respective physical property values according to (1) to (3), and the evaluation results.

[Example 2]
As resin component (A), 87 parts of A-1 obtained in Synthesis Example 1 and as compound (B), a phosphazene compound represented by the above formula (B-1) (phenoxyphosphazene, trade name: Film and molded specimens were prepared in the same manner as in Example 1 except that 13 parts of SPS-100 (manufactured by Otsuka Chemical) were used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

[Comparative Example 1]
In Example 1, a test piece of a film and a molded article was produced in the same manner as in Example 1 except that 100 parts of A-1 as the resin component (A) and 0 part of the compound (B) were used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

[Comparative Example 2]
In Example 1, 95 parts of A-1 was used as the resin component (A), and 1,3-phenylenebisoxy represented by the following formula (C-1) was used as the compound (C) instead of the compound (B). Film and molded specimens were produced in the same manner as in Example 1 except that 5 parts of silenyl phosphate (trade name: PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

[Comparative Example 3]
In Comparative Example 2, 87 parts of A-1 as the resin component (A), and 1,3-phenylenebisdixylenyl phosphate represented by the above formula (C-1) as the compound (C) (trade name: Film and molded specimens were prepared in the same manner as in Comparative Example 2 except that 13 parts of PX-200 (manufactured by Daihachi Chemical Industry) was used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

[Comparative Example 4]
In Comparative Example 2, 80 parts of A-1 as the resin component (A), and 1,3-phenylenebisdixylenyl phosphate represented by the above formula (C-1) as the compound (C) (trade name: Film and molded specimens were produced in the same manner as in Comparative Example 2 except that 20 parts of PX-200 (manufactured by Daihachi Chemical Industry) was used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

[Comparative Example 5]
In Example 1, 70 parts of A-1 as the resin component (A) and 1,3-phenylenebisdixylenyl phosphate represented by the above formula (B-1) (trade name) as the compound (B) : PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) and a test piece of a molded article were produced in the same manner as in Example 1 except that 30 parts were used. Table 1 shows the contents of phosphorus atoms and nitrogen atoms in the composition obtained above, the respective physical property values according to the above (1) to (3), and the evaluation results.

  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 electric / electronic parts” include, for example, a copper-clad laminate of a printed wiring board, an interlayer insulating film of a build-up multilayer wiring layer of a high-density mounting board, and an insulating material of a semiconductor package board 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 (8)

It contains 75 to 99 parts by weight of the cyclic olefin resin (A) and 1 to 25 parts by weight of the compound (B) containing a phosphorus atom and a nitrogen atom represented by the following formula (1) (however, the component (A) and the component The total content of (B) is 100 parts by weight), and the total content of phosphorus atoms and nitrogen atoms in the resin composition is 0.1 to 5% by weight (however, the total resin composition is 100%). The resin composition is characterized in that it is (weight%).

[In Formula (1), each R ¹ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alicyclic carbon atom having 3 to 10 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydrogen group or a substituent. ]   The content of the compound (B) in the total solid content contained in the resin composition is less than 25 wt% (the total solid content in the resin composition is 100 wt%). Resin composition.   3. The resin composition according to claim 1, wherein the glass transition temperature [Tg] is 100 ° C. or higher. The cyclic olefin resin (A) is a (co) polymer having a structural unit derived from a monomer represented by the following formula (2). The resin composition as described.

(In Formula (2), R < ² > -R < ⁵ > represents a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group each independently, R < ² > -R < ⁵ > 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 claim 1, wherein the compound (B) is a compound represented by the following formula (3).

[In Formula (3), each R ⁶ is independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an alicyclic carbon atom having 3 to 10 carbon atoms which may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a hydrogen group or a substituent. q represents an integer of 0 to 5. ]   A molded article formed using the resin composition according to claim 1.   The molded article according to claim 6, wherein the molded article is used for an optical component.   The molded product according to claim 7, wherein the optical component has a film shape, a sheet shape, or a lens shape.