KR20110004789A - Resin composition and optical parts comprising the same - Google Patents

Abstract

PURPOSE: A resin composition is provided to prevent high transparency, low coloring property, and high thermal resistance in a cyclic olefin-based resin. CONSTITUTION: A resin composition includes a cyclic olefin resin(A) and a phenolic compound(B) with a group represented by chemical formula(2) in one molecule. In chemical formula(2), R^14a and R^14b are hydrogen atom or linear or branched C1~10 hydrocarbon group; R^15 and R^16 are independently C1~10 hydrocarbon group; and X shows a methylene group or C2~10 alkylene group.

Description

RESIN COMPOSITION AND OPTICAL PARTS COMPRISING THE SAME

This invention relates to the resin composition which consists of cyclic olefin resin and specific antioxidant.

More specifically, the present invention relates to a resin composition capable of molding an optical part without generating gas and oscillation even under severe processing conditions and without coloring the molded article or generating gel in the molded article.

Since the cyclic olefin resin has high glass transition temperature and light transmittance and has low refractive index anisotropy, the cyclic olefin resin has advantages such as low birefringence compared with the conventional optical film, and is superior in heat resistance, transparency and optical properties. It is attracting attention as.

Thus, using the above-mentioned features, for example, in the field of electronic and optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates and low dielectric materials, and sealing materials such as optical semiconductor encapsulation, cyclic olefins, etc. Application of resin is examined.

On the other hand, in order to meet the recent requirements of weight reduction, miniaturization, and thickness reduction of various members, processing under high temperature and high shear is required. However, the cyclic olefin resin has to be subjected to harsh conditions for processing because of its excellent heat resistance, and addition of an antioxidant is essential to suppress oxidative degradation. Patent Documents 1 and 2 disclose resin compositions containing cyclic olefin resins and various antioxidants, but the antioxidants used do not withstand the processing temperatures of injection molding or extrusion molding, and 1) decompose and volatilize to form a mold or a roll. Contaminants, and 2) decomposed products caused side reactions to produce microgels, which resulted in defects of optical components, and 3) resin processed products discolored to yellow to impair appearance.

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

Japanese Patent No. 2977274 Japanese Laid-Open Patent Publication No. 2002-179875

An object of the present invention is to provide a resin composition which is less in gas generation or dust generation even when processed under high temperature and high shear, and which does not impair the high transparency, low coloration and high heat resistance inherent in the cyclic olefin resin.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the resin composition which solves the said problem is obtained by containing a specific hindered phenol type compound in cyclic olefin resin, and completed this invention.

That is, the following matters are included in this invention.

[1] A cyclic olefin resin (A) having a structural unit derived from the compound represented by the following formula (1), and a phenolic compound (B) having two or more groups represented by the following formula (2) in one molecule Resin composition characterized by the above-mentioned.

(In formula (1), a and b respectively independently represent 0 or 1, and c and d respectively independently represent the integer of 0-2. R <^4> -R <^13> is respectively independently a hydrogen atom; a halogen atom A hydrocarbon group having 1 to 30 carbon atoms, which may be connected by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, or other polar groups, R ¹⁰ and R ¹¹ , or R ¹² And R ¹³ May be integrated to form a divalent hydrocarbon group, and R ¹⁰ or R ¹¹ and R ¹² or R ¹³ may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring.)

(In formula (2), R <^14a> and R <^14b> are respectively independently a hydrogen atom or a linear or branched hydrocarbon group of 1-10 carbon atoms, R <^15> and R <^16> are respectively independently C1-C10 A hydrocarbon group, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms.)

[2] The resin composition according to [1], in which the phenolic compound (B) satisfies the following requirements (B-i) and (B-ii).

(B-i): the molecular weight is 800 or more

(B-ii): The weight loss rate when heated at 300 degreeC for 1 hour under nitrogen is 15% or less

[3] The resin composition according to [1] or [2], wherein the phenol compound (B) is a compound represented by the following Formula (2-1).

(In formula (2-1), R <^14a> and R <^14b> are respectively independently a hydrogen atom or a linear or branched hydrocarbon group of 1-10 carbon atoms, R <^15> and R <^16> are each independently C1-C10 A hydrocarbon group of 10, X represents a methylene group or an alkylene group of 2 to 10 carbon atoms, Y is an n-valent group, a chain hydrocarbon group of 3 to 12 carbon atoms or a cyclic hydrocarbon group of 4 to 8 carbon atoms N is an integer of 1 to 4).

[4] The resin composition according to any one of [1] to [3], wherein the cyclic olefin resin (A) is a ring-opening (co) polymerized hydrogenated body (A-2).

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

[6] A phosphorus-containing compound (C) further satisfying the following requirements (Ci) and (C-ii), wherein the phosphorus-containing compound (C) is based on 100 parts by weight of the cyclic olefin resin (A). 0.005-5 weight part is contained, The resin composition in any one of [1]-[5] characterized by the above-mentioned.

(C-i): the relative molecular mass is 400 or more in the case of a single compound, the weight average molecular weight (Mw) by gel permeation chromatography (GPC) in the polydisperse mixture is 400 or more,

(C-ii): 50% or less in weight loss rate when heated at 250 degreeC for 1 hour under nitrogen.

[7] The resin composition according to [6], wherein the phosphorus-containing compound (C) includes a structure represented by the following Formula (3).

(In formula (3), R <^17> and R <^18> represents a C1-C20 hydrocarbon group each independently, Ar represents an aromatic group, m represents 2 or 3, n represents 0 or 1.)

[8] The above-mentioned [6] or [7], wherein the phosphorus-containing compound (C) contains at least one member selected from compounds represented by the following formulas (3-a) to (3-c): Resin composition.

[9] The resin composition according to [4], wherein a weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the ring-opening (co) polymerized hydrogenated body (A-2) is 30,000 to 200,000.

[10] The resin composition according to [4] or [9], wherein a glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated body (A-2) is 100 to 250 ° C.

[11] [4], [9] or [10], wherein the hydrogenation rate of the carbon-carbon double bond portion excluding the unsaturated bond of the aromatic ring of the ring-opening (co) polymerized hydrogenated body (A-2) is 90% or more. The resin composition described in the above.

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

According to the present invention, by containing a specific phenolic compound in the cyclic olefin resin, even if processed under high temperature or high shear, there is little gas generation and dust generation due to decomposition or volatilization, and high transparency and heat resistance inherent in the cyclic olefin resin And a resin composition that does not impair low colorability.

Moreover, in addition to the said phenolic compound, when a specific phosphorus containing compound is used together, since the color improvement effect is recognized even if content of a phenolic compound is reduced, a quality balance can be adjusted according to the characteristic requested | required.

Therefore, the resin composition of the present invention is very suitable for electronic and optical materials such as optical films, optical disks, optical lenses, optical fibers, transparent plastic base and low dielectric materials, and sealing materials for optical semiconductors.

(Form to carry out invention)

Hereinafter, the optical composition which consists of the resin composition of this invention and the said resin composition is demonstrated.

The resin composition of this invention is a phenolic compound (B) which has two or more groups in 1 molecule of cyclic olefin resin (A) which has a structural unit derived from the compound represented by following formula (1), and following formula (2) in 1 molecule. It is characterized by containing).

In Formula (1), a and b respectively independently represent 0 or 1, and c and d respectively independently represent the integer of 0-2. R ⁴ to R ¹³ each independently represent a hydrogen atom; Halogen atom; A hydrocarbon group of 1 to 30 carbon atoms which may be connected by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; Or other polar groups. R ¹⁰ and R ¹¹ , or R ¹² And R ¹³ May be integrated to form a divalent hydrocarbon group, R ¹⁰ or R ¹¹ , and R ¹² or R ¹³ May combine with each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring.

In formula (2), each of R ^14a and R ^14b independently represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ each independently represent a hydrocarbon having 1 to 10 carbon atoms. A group and X represent a methylene group or the C2-C10 alkylene group.

[Cyclic Olefin Resin (A)]

The cyclic olefin resin (A) used in the present invention is at least one of any of the following polymers A-1 to A-6 derived from the compound represented by the following formula (1).

A-1; Ring-opening (co) polymers of compounds represented by formula (1)

A-2; Ring-opening (co) polymerized hydrogenated body obtained by hydrogenating a ring-opening (co) polymer (A-1)

A-3; The ring-opening (co) polymerized hydrogenated substance which hydrogenated after ring-opening (co) polymer (A-1) by Friedel Crafts reaction

A-4; Addition (co) polymers of compounds represented by formula (1)

A-5; Addition copolymer of the compound represented by Formula (1) with ethylene or monosubstituted ethylene

A-6; The addition copolymer of the compound represented by Formula (1), and at least 1 sort (s) of monomer chosen from a vinyl cyclic hydrocarbon and a cyclic diene, and its addition copolymerization hydrogenated substance.

The compound represented by following formula (1) is demonstrated.

In Formula (1), a and b respectively independently represent 0 or 1, and c and d respectively independently represent the integer of 0-2. R ⁴ to R ¹³ each independently represent a hydrogen atom; Halogen atom; A hydrocarbon group of 1 to 30 carbon atoms which may be connected by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; Or other polar groups. Among these, R ⁴ to R ⁹ preferably represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom Indicates. If R <^4> -R <^9> is said group, the compound represented by Formula (1) can be manufactured in good yield. Any of R ¹⁰ to R ¹³ is a hydrogen atom, preferably R ¹⁰ And R ¹¹ , or R ¹² And R ¹³ Is integrated to form a divalent hydrocarbon group, or R ¹⁰ or R ¹¹ , and R ¹² or R ¹³ Combine with each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring. When R <^10> -R <^13> is said structure, manufacture of the compound represented by Formula (1) is easy, and the cyclic olefin resin (A) obtained from it is high in glass transition temperature (Tg), and is excellent in mechanical strength. .

As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned.

As a hydrocarbon group of 1-30 carbon atoms, For example, Alkyl groups, such as a methyl group, an ethyl group, and a propyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups, such as a vinyl group, an allyl group, and a propenyl group, etc. are mentioned.

The hydrocarbon group having 1 to 30 carbon atoms may be bonded directly to the ring structure, or may be bonded to the ring via a linking group. As a linking group, For example, C1-C10 bivalent hydrocarbon group (for example, alkylene group); Groups having an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom (for example, carbonyl group (-CO-), oxycarbonyl group (-O (CO)-), carbonyloxy group (-COO-), sulfone group (-SO _2- ), ether bond (-O-), thioether bond (-S-), imino group (-NH-), amide bond (-NHCO-, -CONH-) and siloxane bond (-OSi ( R)-) (R is an alkyl group, such as a methyl group and an ethyl group) etc. are mentioned, The coupling group containing two or more may be sufficient.

The other polar group refers to polar groups other than the hydrocarbon group bonded through the linking group. For example, hydroxyl group, alkoxy group, carbonyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, amide group, imide group, trio An organosiloxy group, a triorganosilyl group, an amino group, an acyl group, an alkoxysilyl group, a sulfonyl group, a carboxyl group, etc. are mentioned. Moreover, specifically, as said alkoxy group, a methoxy group, an ethoxy group, etc .; Examples of the carbonyloxy group include alkylcarbonyloxy groups such as acetoxy group and propionyloxy group, and arylcarbonyloxy groups such as benzoyloxy group; As an alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, etc .; Examples of the aryloxycarbonyl group include phenoxycarbonyl group, naphthyloxycarbonyl group, fluorenyloxycarbonyl group and biphenylyloxycarbonyl group; Examples of the triorganosiloxy group include trimethylsiloxy group, triethylsiloxy group, and the like; Examples of the triorganosilyl group include trimethylsilyl group and triethylsilyl group; As an amino group, Primary amino group; Examples of the alkoxysilyl group include trimethoxysilyl group, triethoxysilyl group, and the like.

In the compound represented by the formula (1), a and b are each independently 0 or 1, preferably a = b = 0. c and d are each independently an integer of 0 to 2, preferably 0 to 1, more preferably c = 0 and d = 0 or 1. If a-d is this range, it is preferable at the point of availability of the raw material for manufacturing the compound represented by Formula (1), economical efficiency, and productivity of the compound represented by Formula (1).

As a specific example of the compound represented by Formula (1),

Bicyclo [2.2.1] hepto-2-ene,

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

Tricyclo [4.3.0.1 ^2,5 ] -deca-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

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

5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hepto-2-ene , 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-ethylidenebicyclo [2.2.1] hepto-2-ene, 5-cyanobicyclo [2.2.1 ] Hepto-2-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] -3-dodecene, 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-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-isopro Foxycarbonyltetracyclo [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-phenoxy-carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8- (1-naphthoxy) carbonyl tetrahydro four Chloride [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8- (2-naphthoxy) carbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene , 8- (4-phenylphenoxycarbonyl) tetracyclo [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, 8-methyl-8-phenoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl-8- ( 1-naphthoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methyl-8- (2-naphthoxy) carbonyltetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10 ] -3-dodecene, 8-methyl-8- (4-phenylphenoxy) carbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

Pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] -3-hexadecene

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

Heptacyclo [8.8.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0 ^12,17 ] -5- ^heneicosene , 5- ^{phenylbicyclo} [2.2.1] hepto-2 -Ene, 5-phenyl-5-methylbicyclo [2.2.1] hepto-2-ene, 8-phenyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 5-n -Butylbicyclo [2.2.1] hepto-2-ene, 5-n-hexylbicyclo [2.2.1] hepto-2-ene, 5- (2-cyclohexenyl) bicyclo [2.2.1] hepto 2-ene, 5-n-octylbicyclo [2.2.1] hepto-2-ene, 5-n-decylbicyclo [2.2.1] hepto-2-ene, 5-isopropylbicyclo [2.2. 1] hepto-2-ene, 5- (1-naphthyl) bicyclo [2.2.1] hepto-2-ene, 5- (2-naphthyl) bicyclo [2.2.1] hepto-2-ene, 5- (2-naphthyl) -5-methylbicyclo [2.2.1] hepto-2-ene, 5- (4-biphenyl) bicyclo [2.2.1] hepto-2-ene, 5- (4 -Biphenyl) -5-methylbicyclo [2.2.1] hepto-2-ene, 5-aminomethylbicyclo [2.2.1] hepto-2-ene, 5-trimethoxysilylbicyclo [2.2.1 ] Hepto-2-ene, 5-triethoxysil Reelbicyclo [2.2.1] hepto-2-ene, 5-tri-n-propoxysilylbicyclo [2.2.1] hepto-2-ene, 5-trin-butoxysilylbicyclo [2.2.1 ] Hepto-2-ene, 5-chloromethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexenylbicyclo [ 2.2.1] hepto-2-ene, 5-fluorobicyclo [2.2.1] hepto-2-ene, 5-fluoromethylbicyclo [2.2.1] hepto-2-ene, 5-trifluoro Methylbicyclo [2.2.1] hepto-2-ene, 5,5-difluorobicyclo [2.2.1] hepto-2-ene, 5,6-difluorobicyclo [2.2.1] hepto- 2-ene, 5,5-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2- N, 5-methyl-5-trifluoromethylbicyclo [2.2.1] hepto-2-ene, 5,5,6-trifluorobicyclo [2.2.1] hepto-2-ene, 5,5 , 6,6-tetrafluorobicyclo [2.2.1] hepto-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-dode Sen, 8-trifluoromethyltetracyclo [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, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene

And [fluorene-9,8'-tricyclo [4.3.0.1 ^2,5 ] [3] decene] and the like, and particularly preferably bicyclo [2.2.1] hepto-2-ene, Tricyclo [4.3.0.1 ^2,5 ] -3-decene, tricyclo [4.3.0.1 ^2,5 ] -deca-3,8-diene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]- 3-dodecene, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Ethylidenebicyclo [2.2.1] hepto-2-ene, 8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8-methoxycarbonyl-8-methyl Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 5-phenylbicyclo [2.2.1] hepto-2-ene.

The compound represented by said formula (1) is used individually or in combination of 2 or more types.

(Copolymerizable monomer)

As a copolymerizable monomer used for synthesize | combining said (A-1)-(A-6), well-known cycloolefin, such as cyclobutene, cyclopentene, cycloheptene, and cyclooctene, is mentioned, for example.

In this invention, the said cyclic olefin resin can be obtained by a well-known method, For example, Unexamined-Japanese-Patent No. 01-132626, Unexamined-Japanese-Patent No. 2006-77257, and Unexamined-Japanese-Patent No. 2008- What is obtained by the method of 955 can be used.

Among these cyclic olefin resins (A-1)-(A-6), Preferably they are (A-2)-(A-5), Especially preferably, they are (A-2). The ring-opening (co) polymerized hydrogenated body (A-2) is preferable because of its excellent heat resistance, mechanical strength, processability, transparency, productivity, and the like.

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

Tetrahydrofuran of the cyclic olefin resin (A) is used as a solvent, and the weight average molecular weight (Mw) by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably 30,000 to 200,000, and more preferably 32,000 to 180,000, Especially preferably, it is the range of 35,000-160,000, Molecular weight distribution (Mw / Mn) becomes like this. Preferably it is 1.5-4.0, More preferably, it is 1.7-3.7, Especially preferably, it is 2.0-3.5. Moreover, the weight average molecular weight (Mw) of standard polystyrene conversion by gel permeation chromatography (GPC) of the ring-opening (co) polymerization hydrogenated body (A-2) which is a preferable form of cyclic olefin resin (A) becomes like this. 200,000, More preferably, it is 31,000-150,000, Especially preferably, it is 32,000-120,000. When the weight average molecular weight (Mw) of a ring-opening (co) polymerized hydrogenated body (A-2) exists in the said range, since workability and strength are compatible, it is preferable.

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

As glass transition temperature (Tg) of the said cyclic olefin resin (A), it is 110-350 degreeC normally, Preferably it is 110-250 degreeC, More preferably, it is 110-220 degreeC, Especially preferably, it is 110-200 degreeC. When Tg is less than 110 degreeC, it may deform | transform at the time of use under high temperature conditions. On the other hand, when Tg exceeds 350 degreeC, shaping | molding process may become difficult. That is, when Tg exceeds 350 degreeC, the heating temperature at the time of shaping | molding process must be made high and the possibility that resin may deteriorate by heat may increase. Moreover, the glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated body (A-2) which is a preferable form of cyclic olefin resin (A) becomes like this. Preferably it is 100-250 degreeC, More preferably, it is 105-220 degreeC, Especially preferably, it is 110-210 degreeC. When the glass transition temperature (Tg) of the ring-opening (co) polymerized hydrogenated body (A-2) is in the above range, it is preferable because melt processing is easy and has practical heat resistance.

When hydrogenating the said cyclic olefin resin (A), it is preferable that the hydrogenation rate of the carbon-carbon double bond except the unsaturated bond of an aromatic ring is 90% or more, and it is more preferable that it is 95% or more. When hydrogenation rate exists in the said range, heat resistance and coloring property become more favorable. Moreover, you may also hydrogenate the unsaturated bond of an aromatic ring as needed.

As the cyclic olefin resin (A), specific hydrocarbon resins and specific known thermoplastics described in, for example, Japanese Patent Application Laid-Open No. 9-221577 and Japanese Patent Application Laid-open No. Hei 10-287732 as necessary. You may mix | blend resin and a thermoplastic elastomer, a rubbery polymer, organic microparticles | fine-particles, an inorganic fine particle, etc. in the quantity of 0 to 60 weight%.

Phenol-Based Compound (B)

The phenolic compound (B) used by this invention has two or more groups represented by following formula (2) in 1 molecule, It is characterized by the above-mentioned.

In formula (2), R ^14a and R ^14b each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and R ¹⁵ and R ¹⁶ each independently represent 1 to 10 carbon atoms. Hydrocarbon group is represented. As said C1-C10 hydrocarbon group, alkyl groups, such as a methyl group, an ethyl group, a propyl group, n-butyl group, isobutyl group, and t-butyl group, are mentioned, for example. Among them, t-butyl group is preferable as R ¹⁵ , and methyl group is preferable as R ¹⁶ .

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

Moreover, it is preferable that a phenol type compound (B) does not have an aliphatic ester structure. This is because the aliphatic ester structure is insufficient in thermal stability, so that it may decompose at the time of high temperature processing and may generate microgels by reacting the generated alcohol or carboxylic acid with the resin composition. In addition, an aliphatic ester structure is represented by -CO-O-R, and R is a linear or branched alkyl group.

It is preferable that the said phenol type compound (B) is a compound represented by following formula (2-1).

In formula (2-1), R <^14a> , R <^14b> , R <^15> and R <^16> are synonymous with said Formula (2), Y is an n-valent group, C3-C12 linear hydrocarbon group, or carbon number of atoms 4-8 cyclic hydrocarbon group is represented, n is an integer of 1-4.

Propane, butane, pentane, hexane, heptane, and octane etc. are mentioned as said C3-C12 linear hydrocarbon group, n hydrogen of these groups is substituted by the group represented by Formula (2). Moreover, as said chain hydrocarbon group, it may have a substituent other than the group represented by Formula (2).

Examples of the cyclic hydrocarbon group having 4 to 8 carbon atoms include cyclobutane, cyclopentane, cyclohexane, cycloheptane and cyclooctane, and n hydrogens in these groups are substituted with a group represented by formula (2). . Moreover, as said chain hydrocarbon group, it may have a substituent other than the group represented by Formula (2).

Specifically as said phenolic compound (B), 1,1,3-tris [2-methyl-4- [3- (3, 5-di-t-butyl-4) represented by a following formula (2-a) -Hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane.

Phenolic compounds are generally known as antioxidants, and when there are few phenolic structural moieties with respect to molecular weight, it is known that the antioxidant effect, that is, the radical replenishment ability, which is the original purpose, becomes small.

The phenolic compound (B) used in the present invention has a hindered structure in addition to having two or more phenolic structural moieties such as the group represented by the formula (2) in one molecule, so that side reactions of the antioxidant are suppressed.

It is preferable to satisfy the requirements (B-i) and (B-ii) of the phenolic compound (B).

(B-i): The molecular weight is 800 or more. The phenolic compound (B) may be a mixture of a compound having various molecular weights (hereinafter referred to as a "polydisperse mixture") other than a single compound. In the case of a single compound, the relative molecular mass is preferably 800 or more, more preferably 800 to 3000, particularly preferably 850 to 2800, particularly preferably 900 to 2500. On the other hand, in a polydisperse mixture, the weight average molecular weight (Mw) of standard polystyrene conversion by gel permeation chromatography (GPC) becomes like this. Preferably it is 800 or more, More preferably, it is 800-4000, Especially preferably, 850-3500, Especially preferably, it is 900-3000, and molecular weight distribution (Mw / Mn) is 1.01-3.0, Preferably it is 1.02-2.7, More preferably, it is 1.03-2.5. If the molecular weight and molecular weight distribution of a phenolic compound (B) exist in the said range, volatilization of the phenolic compound (B) at the time of processing of a resin composition will be fully suppressed, and antioxidant will have sufficient transferability also in a resin molded article. Therefore, oxidative degradation is suppressed over a long period of time. In the present invention, as the phenolic compound (B), only a single compound may be used or a polydisperse mixture may be used. In addition, relative molecular mass means the mass of a molecule | numerator when the mass of carbon is set to 12.

(B-ii): The weight loss rate when heated at 300 degreeC for 1 hour under nitrogen is 15% or less, More preferably, it is 13% or less, Especially preferably, it is 10% or less. If the weight reduction rate is in the above range, mold contamination and roll contamination by the thermal decomposition products can be suppressed. In addition, the method of obtaining the weight reduction rate will be described. After the sample is heated to 300 ± 5 ° C. from room temperature at a temperature increase rate of 40 ° C./min using TG / DTA in a nitrogen atmosphere, the weight is measured for 1 hour. The weight reduction rate (%) is obtained from the initial weight and the weight after heating.

The addition amount of the said phenol type compound (B) is 0.01-3 weight part normally with respect to 100 weight part of cyclic olefin resin (A), Preferably it is 0.02-2.5 weight part, More preferably, it is 0.03-2 weight part. . If the addition amount of a phenol type compound (B) exists in the said range, oxidative deterioration of the resin composition of this invention can fully be prevented. Moreover, although the said phenol type compound (B) is comparatively low in volatility, when it adds beyond the said range, there exists a tendency for the quantity of volatile components to increase. In addition, the antioxidant prevents the oxidation of the resin under high temperature, and may deteriorate and color itself, and the addition beyond the necessary amount that can prevent the oxidation of the resin may adversely affect. For this reason, it is preferable to make the addition amount of a phenol type compound (B) into the said range.

Phosphorus-containing compound (C)

The resin composition of this invention may contain phosphorus containing compound (C) other than cyclic olefin resin (A) and a phenol type compound (B). Although the phosphorus containing compound (C) used by this invention is not very high in itself, the color and process stability of a resin composition can be improved. Here, processing stability means the minimum suppression of gel generation | occurrence | production, smoke, and a dust, etc. at the time of processing a resin composition, for example. In addition, a phosphorus containing compound is known as an antioxidant normally including the said phosphorus containing compound (C).

As a phosphorus containing compound (C), if a following thing (C-i) and (C-ii) are satisfied, a structure will not be specifically limited.

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

(C-ii): The weight reduction rate when the phosphorus-containing compound (C) is heated at 250 ° C. for 1 hour under nitrogen is preferably 50% or less, more preferably 40% or less, particularly preferably 30% It is In addition, the method of obtaining the weight reduction rate is described. After the sample is heated up to 250 ± 3 ° C. from room temperature at a temperature increase rate of 40 ° C./min using TG / DTA, and held for 1 hour, the weight is measured. The weight reduction rate is obtained from the initial weight and the weight after heating.

It is preferable that the said phosphorus containing compound contains the structure represented by following formula (3).

In formula (3), R <^17> and R <^18> represents a C1-C20 hydrocarbon group each independently, Ar represents an aromatic group, m represents 2 or 3, n represents 0 or 1.

Examples of the hydrocarbon group include an alkyl group and an aryl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, isobutyl group, t-butyl group, etc. are mentioned, for example. Moreover, since the hydrogen atom of these alkyl groups may be substituted by the other substituent and especially substituted by a hindered phenol group, since coloring can fully be suppressed, it is preferable. A phenyl group, a biphenyl group, a naphthyl group, etc. are mentioned as an aryl group. In addition, the hydrogen atom of these aryl groups may be substituted by the other substituent, For example, you may form said structure (3) and a target structure through a biphenylene group like the compound represented by following formula (4). Such a structure is preferable because its volatility can be reduced by increasing the molecular weight while maintaining the effect of the phosphorus antioxidant.

As an aromatic group, a phenyl group, a naphthyl group, anthracenyl group, etc. are mentioned, for example, Preferably a phenyl group is mentioned. The hydrogen atoms of these aromatic groups may be substituted with other substituents, and in particular, when substituted with a high-volume group such as a t-butyl group, hydrolysis resistance and heat resistance are preferable. In addition, the aromatic group may be bonded directly to R ¹⁸ or through a substituent.

Specific examples of the phosphorus-containing compound (C) include tris (2,4-di-t-butylphenyl) phosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenyl Mixtures based on rendiphosphonite (for example, Clariant Japan Co., Ltd .; Hostanox P-EPQ), Tetrakis (2,4-di-t-butylphenyl-5-methyl) -4, Mixture mainly containing 4'-biphenylenediphosphonite (for example, Osaki Kogyo Co., Ltd .; GSY-P101), 6- [3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine, bis (2,6-di-t-butyl- 4-methylphenyl) pentaerythritol diphosphite, bis (2, 4- dicumylphenyl) pentaerythritol diphosphite, etc. are mentioned. Among them, the tris (2,4-di-t-butylphenyl) phosphite represented by the formula (3-a) and 6- represented by the formula (3-b) are particularly preferred in terms of low volatility and low colorability. [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] Dioxaphosphine and the tetrakis (2, 4- di-t- butylphenyl-5-methyl) -4, 4'- biphenylenediphosphonite shown by Formula (3-c) are mentioned.

These phosphorus containing compounds (C) can also be used individually by 1 type or in combination of 2 or more types. When using it in combination of 2 or more type, it is especially preferable to use the compound shown by Formula (3-a), (3-b) or (3-c) as a main component.

The addition amount of the phosphorus-containing compound (C) is preferably 0.005 to 5 parts by weight, more preferably 0.007 to 4 parts by weight, particularly preferably 0.01 to 3 parts by weight based on 100 parts by weight of the cyclic olefin resin (A). It is wealth. When the addition amount of phosphorus containing compound (C) exists in the said range, the hue of a resin composition can be kept favorable, a gel formation can be prevented, and smoke and dust can be suppressed to the minimum.

Moreover, when phosphorus containing compound (C) is used together, since the color improvement effect is recognized even if content of the said phenolic compound (B) is reduced, a quality balance can be controlled according to the characteristic requested | required.

[Resin composition]

The resin composition of this invention can be manufactured by melt-kneading a cyclic olefin resin (A), a phenol type compound (B), and a phosphorus containing compound (C) as needed.

In the resin composition, a light stabilizer, an ultraviolet absorber, an infrared absorber, an antistatic agent, a dispersant, a processability improving agent, a chlorine trapping agent, a flame retardant, a crystallization nucleating agent, an antiblocking agent, and an antifogging agent within the range in which the effects of the present invention are not impaired. Iii), known additives such as mold release agents, dyes, pigments, fluorescent brighteners, organic fillers, inorganic fillers, neutralizing agents, lubricants, disintegrating agents, metal deactivators, antifouling agents and antibacterial agents, and resins such as thermoplastic elastomers may be added. .

Moreover, kneading apparatuses, such as kneading | mixing and dispersing machines, such as a roll kneader, a mixer, a homo mixer, or a sand mill, are used for melt kneading.

[Optical parts]

Since the resin composition of the present invention has high transparency, low colorability, and high heat resistance, it is very suitable for electronic and optical materials such as optical films, optical discs, optical lenses, optical fibers, transparent plastic bases and low dielectric materials, and sealing materials for optical semiconductors. Suitable.

(Example)

Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

The analysis method used by the Example and the comparative example is shown below.

<Analysis method>

(1) GPC: gel permeation chromatography apparatus (HLC-8220GPC manufactured by Tosoh Corporation, column; guide column HXL-H manufactured by Toso Corporation, TSK gel G7000HXL, two TSK gel GMHXL, and TSK gel G2000HXL) Eluent; tetrahydrofuran, flow rate; 1 mL / min, sample concentration; 0.7 to 0.8 wt%, sample injection amount; 70 μL, measurement temperature; 40 ° C., detector; RI (40 ° C.), standard material; Tosoh Inc. The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the standard polystyrene conversion were measured using the TSK standard polystyrene manufactured by Kaisha. In addition, Mn is the number average molecular weight of standard polystyrene conversion.

(2) NMR: ¹ H-NMR was measured in deuterated chloroform using the superconducting nuclear magnetic resonance absorption apparatus (NMR, Bruker Co., Ltd. brand name: AVANCE500), and the copolymerization composition ratio and the hydrogenation rate were calculated | required.

(3) Logarithmic viscosity: It measured at the sample concentration of 0.5 g / dL, and temperature of 30 degreeC in chloroform using the ubelode viscometer.

(4) Glass transition temperature (Tg): The extrapolation glass transition temperature was calculated | required according to Japanese Industrial Standard K7121 using the differential scanning calorimeter (SII nanotechnology company make, brand name: DSC6220).

(5) Scanning electron microscope: JSM6360LA type | mold by Nippon Denshi Corporation was used.

Synthesis Example 1

8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene 100 g, represented by the following formula (1-a) as a monomer, 1-hexene 7.2 as molecular weight regulator g and 200 g of toluene were put into the reaction container which carried out the nitrogen substitution, and it heated at 80 degreeC.

0.21 mL of toluene solution (0.6 mol / L) of triethylaluminum and 0.86 mL of toluene solution (0.025 mol / L) of methanol modified tungsten hexachloride (WCl ₆ ) were added to this, and the ring-opening polymer was made to react at 80 degreeC for 1 hour. Got.

0.04 g of chlorohydride carbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ), which is a hydrogenation catalyst, is added to the obtained ring-opening polymer solution, and the hydrogen gas pressure is 9-. It was made to react at 160-165 degreeC for 3 hours as 10 Mpa.

After the reaction was completed, a hydrogenated body was obtained by precipitating the obtained reaction mixture in a large amount of methanol. This hydrogenated substance is called 1A.

As for the yield of obtained hydrogenated substance 1A, 90g (yield 90%), glass transition temperature (Tg) are 163 degreeC, weight average molecular weight (Mw) is 6.7x10 <^4> , molecular weight distribution (Mw / Mn) Was 5.0, the logarithmic viscosity was 0.45 dL / g, and the hydrogenation rate was 99.0% or more.

Synthesis Example 2

144 g of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene represented by formula (1-a), 2- represented by formula (1-b) 6 g of norbornene and 14.4 g of 1-hexene and 225 g of toluene were put into a nitrogen-substituted reaction container as a molecular weight regulator, and it heated at 80 degreeC.

0.34 mL of toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of toluene solution (0.025 mol / L) of methanol-modified tungsten hexachloride (WCl ₆ ) were added thereto and reacted at 80 ° C. for 1 hour to open the air. The coalescence was obtained.

0.06 g of chlorohydride carbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ), which is a hydrogenation catalyst, is added to the obtained ring-opening copolymer solution, and the hydrogen gas pressure is 9 It was -10 MPa and made it react at 160-165 degreeC for 3 hours.

After the reaction was completed, a hydrogenated product was obtained by precipitating the obtained product in a large amount of methanol. This hydrogenated substance is called 2A.

As for the yield of obtained hydrogenated substance 2A, 90g (yield 90%), glass transition temperature (Tg) are 154 degreeC, weight average molecular weight (Mw) is 7.4x10 <^4> , molecular weight distribution (Mw / Mn) is 4.2, logarithm number The viscosity was 0.55 dL / g and the hydrogenation rate was 99.0% or more, and the copolymerization composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] was 95.8 / 4.2 (weight ratio).

Synthesis Example 3

8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene 113.2 g shown in formula (1-a), 2 shown in formula (1-b) -1.5 g of norbornene, 35.3 g of dicyclopentadiene represented by the following formula (1-c), and 20.5 g of 1-hexene and 225 g of toluene as nitrogen molecular weight regulators were put into the reaction container which carried out the nitrogen substitution, and it heated at 80 degreeC.

0.34 mL of toluene solution (0.6 mol / L) of triethylaluminum and 1.39 mL of toluene solution (0.025 mol / L) of methanol-modified tungsten hexachloride (WCl ₆ ) were added thereto and reacted at 80 ° C. for 1 hour to open the air. The coalescence was obtained.

(4-pentylbenzoyloxy) carbonyl (hydride) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), which is a hydrogenation catalyst, to the obtained ring-opening copolymer solution ( 0.06 g of CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) was added, the temperature was raised to 90 ° C., and the hydrogen gas pressure was set to 9 to 10 MPa, further 160 to 165 It heated up to ° C and reacted for 3 hours.

After the reaction was completed, a hydrogenated product was obtained by precipitating the obtained product in a large amount of methanol. This hydrogenated substance is called 3A.

As for the yield of obtained hydrogenated body 3A, 90 g (yield 90%), glass transition temperature (Tg) are 141 degreeC, weight average molecular weight (Mw) is 4.4x10 <^4> , molecular weight distribution (Mw / Mn) is 5.1, logarithm number The viscosity is 0.41 dL / g, the hydrogenation rate is 99.0% or more, and the copolymer composition ratio [structure derived from (1-a)] / [structure derived from (1-b)] / [structure derived from (1-c)] is 75.3. /1.1/23.6 (weight ratio).

Synthesis Example 4

8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene shown in the formula (1-a) to 133.5 g, and the formula (1-b) 16.5 g of 2-norbornene shown and 15.4 g of 1-hexene and 225 g of toluene were put into the reaction container which carried out the nitrogen substitution as a molecular weight regulator, and it heated at 80 degreeC.

0.34 mL of toluene solution of triethylaluminum (0.6 mol / L) and 1.37 mL of methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added to this, and the ring-opening copolymer was obtained by making it react at 80 degreeC for 1 hour.

Subsequently, 0.06 g of chlorohydride carbonyltris (triphenylphosphine) ruthenium (RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ) as a hydrogenation catalyst was added to the obtained ring-opening copolymer solution, and hydrogen gas pressure Was made into 9-10 Mpa, and it was made to react at 160-165 degreeC for 3 hours.

After the reaction was completed, a hydrogenated product was obtained by precipitating the obtained product in a large amount of methanol. Let this hydrogenated substance be 4A [glass transition temperature (Tg) = 126 degreeC, weight average molecular weight (Mw) = 5.0x10 <^4> , molecular weight distribution (Mw / Mn) = 4.2, logarithmic viscosity 0.43dL / g, quantity 90g (Yield 90%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more, and copolymerization composition ratio was [structure derived from (1-a)] / [structure derived from (1-1-)) = 89/11 (weight ratio). .

Synthesis Example 5

42.0 g of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene represented by formula (1-a) and shown by following formula (1-d) 28.0 g of 1,4,4a, 9a-tetrahydro-1,4-methanofluorene and 1-hexene 11.2 g and 105 g of toluene were put into the reaction vessel which carried out the nitrogen substitution as a molecular weight regulator, and it heated at 80 degreeC.

To this was added 1.15 mL of a toluene solution of triethylaluminum (0.2 mol / L) and 0.67 mL of a toluene solution (0.050 mol / L) of methanol-modified tungsten hexachloride (WCl ₆ ). The coalescence was obtained.

251 g of toluene was further diluted and diluted in the obtained ring-opening copolymer solution, and (4-pentyl benzoyloxy) carbonyl (hydride) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ CH ₂ CH) which is a hydrogenation catalyst 0.02 g of ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₂ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, and the hydrogen gas pressure is set to 9 to 10 MPa, further 160 to 165 It heated up to ° C and reacted for 3 hours.

After the reaction was completed, a hydrogenated product was obtained by precipitating the obtained product in a large amount of methanol. This hydrogenated substance is 5 A. [glass transition temperature (Tg) = 161 degreeC, weight average molecular weight (Mw) = 8.3x10 <^4> , molecular weight distribution (Mw / Mn) = 3.8, logarithmic viscosity 0.51 dL / g, quantity 63 g (Yield 90%)]. The hydrogenation rate of this hydrogenated substance calculated | required by NMR measurement was 99.0% or more, and the copolymerization composition ratio was [structure derived from (1-a)] / [structure derived from (1-d)] = 59/41 (weight ratio). .

　(1-d)

(1-d)

[Synthesis Example 6]

45.0 g of dicyclopentadiene shown in said Formula (1-c) and 0.3 g of 1-hexene and 103 g of cyclohexanes were put into the reaction container which carried out the nitrogen substitution as a molecular weight regulator, and it heated at 70 degreeC.

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

456.4 g of cyclohexane was added and diluted in the obtained ring-opening copolymer solution, and (4-pentyl benzoyloxy) carbonyl (hydride) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ CH) which is a hydrogenation catalyst 0.05 g of ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, and the hydrogen gas pressure is 9 to 10 MPa, further 160 It heated up to -165 degreeC and made it react for 3 hours.

After the reaction was completed, a hydrogenated product was obtained by precipitating the obtained product in a large amount of methanol. This hydrogenated substance is called 6A. 40g (yield 89%) and glass transition temperature (Tg) of the obtained hydrogenated body 6A were 100 degreeC. Molecular weight was measured by measuring GPC using o-dichlorobenzene. As for weight average molecular weight (Mw), 6.8x10 <^4> , molecular weight distribution (Mw / Mn) were 1.8, and the hydrogenation rate was 99.0% or more.

[Synthesis Example 7]

31.5 g of dicyclopentadiene shown by said formula (1-c), tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene shown by following formula (1-e), 38.5 g, molecular weight modifier As the reaction vessel, 0.4 g of 1-hexene and 165 g of cyclohexane were put into a nitrogen-substituted reaction vessel, and heated to 70 ° C.

0.96 mL of toluene solution (1.0 mol / L) of triisobutylaluminum, 0.72 mL of cyclohexane solution (1.0 mol / L) of 2-butanol, 2.39 mL of toluene solution (0.1 mol / L) of acetone, and tungsten chloride A ring-opening copolymer was obtained by adding 9.57 mL of toluene solution (0.025 mol / L) of (WCl ₆ ) and reacting at 70 ° C. for 1 hour.

To the obtained ring-opening copolymer solution, 633 g of cyclohexane was further added and diluted, and (4-pentylbenzoyloxy) carbonyl (hydride) bis (triphenylphosphine) ruthenium (RuH (OCO-Ar-CH ₂ CH ₂ ), which is a hydrogenation catalyst, was diluted. 0.04 g of CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ ) (Ar represents a paraphenylene group) is added, and the hydrogen gas pressure is 9-10 MPa. It heated up to 165 degreeC and made it react for 3 hours.

After the completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain an additive. This hydrogenated substance is called 7A. The yield of the obtained hydrogenated substance 7A was 65 g (yield 93%), and the glass transition temperature (Tg) was 130 ° C. Molecular weight was measured by measuring GPC using o-dichlorobenzene. As for weight average molecular weight (Mw), 4.5x10 <^4> , molecular weight distribution (Mw / Mn) were 2.7, and the hydrogenation rate was 99.0% or more. The copolymerization composition ratio was [structure derived from ((1-c)] / [structure derived from (1-e))] = 46/54 (weight ratio).

　　(1-e)

(1-e)

Example 1

To 100 g of hydrogenated substance (1A) obtained in Synthesis Example 1, 1,1,3-tris [2-methyl-4- [3- (3, 0.3 g of 5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -5-t-butylphenyl] butane and kneading for 30 minutes at 280 ° C under air in a Labo Plastomill And the resin composition was obtained.

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

[Example 2]

In Example 1, the resin composition was obtained like Example 1 except having used the hydrogenated body 2A obtained by the synthesis example 2 instead of the hydrogenated body 1A.

Example 3

In Example 1, the resin composition was obtained like Example 1 except having used the hydrogenated body 3A obtained by the synthesis example 3 instead of the hydrogenated body 1A.

Example 4

In Example 3, the resin composition was obtained like Example 3 except having changed the quantity of the compound shown by Formula (2-a) from 0.3g to 1.0g.

Example 5

In Example 3, in addition to the compound represented by a hydrogenated body (3A) and a formula (2-a), the tris (2,4-di shown by following formula (3-a) as a phosphorus containing compound (C) further A resin composition was obtained in the same manner as in Example 3 except that 0.3 g of -t-butylphenyl) phosphite was added.

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

Example 6

In Example 5, 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy represented by the following formula (3-b) instead of the compound represented by formula (3-a). The resin composition was obtained like Example 5 except having used] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphine.

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

Example 7

In Example 5, instead of the compound represented by formula (3-a), tetrakis (2,4-di-t-butylphenyl-5-methyl) -4,4 'represented by the following formula (3-c): The resin composition was obtained like Example 5 except having used the phosphorus antioxidant (brand name; GSY-P101 by Osaki Kogyo Co., Ltd.) which has biphenylenediphosphonite as a main component.

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

Example 8

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

Example 9

In Example 1, the resin composition was obtained like Example 1 except having used the hydrogenated body 5A obtained by the synthesis example 5 instead of the hydrogenated body 1A.

Moreover, it shows in Table 3 about preparation of a resin composition.

Example 10

In Example 1, the resin composition was obtained like Example 1 except having used the hydrogenated body 6A obtained by the synthesis example 6 instead of the hydrogenated body 1A.

Moreover, it shows in Table 3 about preparation of a resin composition.

Example 11

In Example 1, the resin composition was obtained like Example 1 except having used the hydrogenated body 7A obtained by the synthesis example 7 instead of the hydrogenated body 1A.

Moreover, it shows in Table 3 about preparation of a resin composition.

Comparative Example 1

In Example 3, the resin composition was obtained like Example 3 except having used the compound shown by following formula (2'-a) instead of the compound shown by Formula (2-a).

In addition, the property of the compound shown by Formula (2'-a) is shown in Table 1, and Table 2 is shown about preparation of a resin composition.

Comparative Example 2

In Example 4, the resin composition was obtained like Example 4 except having used the compound 1.5g shown by Formula (2'-a) instead of the compound 1.0g shown by Formula (2-a).

Comparative Example 3

In Example 3, the resin composition was obtained like Example 3 except having used the compound shown by following formula (2'-b) instead of the compound shown by Formula (2-a).

In addition, the property of the compound shown in Formula (2'-b) is shown in Table 1.

[Comparative Example 4]

In Example 3, the resin composition was obtained like Example 3 except having used the compound shown by following formula (2'-c) instead of the compound shown by Formula (2-a).

In addition, the property of the compound shown in Formula (2'-c) is shown in Table 1.

<Evaluation method>

The following evaluation was performed about the resin composition obtained by the Example and the comparative example. The results are shown in Tables 2 and 3.

(1) Smoke evaluation: The smoke property at the time of platomil kneading was visually observed based on the following criteria.

○ did not smoke

△ hardly smoke

× smoked

(2) Color evaluation: After melt | dissolving a resin composition in toluene to make the solution of 10 weight% of concentration, yellowness (YI) was measured and evaluated. The measurement was performed 3 times of C-light 2 ° field-permeation measurements using SM color computer SM-7-CH made from Suga Shikenki Co., Ltd., and calculated | required the average value (Measurement sample: 20 g of sample solution used, measuring cell: 60 mm inside diameters). , Cylindrical glass cells 30 mm high).

(3) Gel evaluation: After melt | dissolving a resin composition in toluene to make the solution of 10 weight% of concentration, it filtered with the PTFE filter of 1.0 micrometer pore diameter. After filtration, the filter was baked under air at 260 ° C. for 30 minutes to oxidize (brown) the toluene insoluble component (gel) remaining on the filter, and count the number with a stereomicroscope to obtain 1 g of the resin composition from the filtration area and the amount of filtration. The number of gels in it was calculated, and less than 100 pieces / g was made into (circle) and 500 pieces / g or more into x. In addition, a gel means the organic substance which existed planarly on a filter, and turned brown by baking, and the thing of fibrous form and the three-dimensional form as a foreign substance derived from the environment was not counted as gel number.

(4) Transparency evaluation: The transparency of the resin composition obtained by platomil kneading was visually observed based on the following criteria.

○ was transparent

△ slightly cloudy

× cloudy

From the result of Table 2, the resin composition which added the specific phenolic compound (B) to the cyclic olefin resin (A) improves all the problems of coloring, gel formation, and smoke at the time of processing which were conventionally considered a problem. It can be seen that. For example, when the phosphorus containing compound (C) is used together from the comparison result of Examples 4 and 7, since the color improvement effect is recognized even if the addition amount of a phenolic compound (B) is reduced, according to the characteristic required You can adjust the quality balance.

Claims (12)

It contains cyclic olefin resin (A) which has a structural unit derived from the compound represented by following formula (1), and the phenolic compound (B) which has two or more groups represented by following formula (2) in 1 molecule. Resin composition made into:

(In formula (1), a and b respectively independently represent 0 or 1, c and d respectively independently represent the integer of 0-2; R <^4> -R <^13> is respectively independently a hydrogen atom; a halogen atom A hydrocarbon group having 1 to 30 carbon atoms which may be connected by a group having an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom; or other polar groups; R ¹⁰ and R ¹¹ , or R ¹² And R ¹³ May be integrated to form a divalent hydrocarbon group, R ¹⁰ or R ¹¹ , and R ¹² or R ¹³ May combine with each other to form a monocyclic or polycyclic carbocycle or heterocycle);

(In formula (2), R <^14a> and R <^14b> are respectively independently a hydrogen atom or a linear or branched hydrocarbon group of 1-10 carbon atoms, R <^15> and R <^16> are respectively independently C1-C10 Hydrocarbon group, X represents a methylene group or an alkylene group having 2 to 10 carbon atoms. The method of claim 1,
Resin composition characterized in that the phenolic compound (B) meets the following requirements (Bi) and (B-ii):
(Bi): molecular weight 800 or more
(B-ii): The weight reduction rate when heated at 300 degreeC for 1 hour under nitrogen is 15% or less. The method of claim 1,
The said phenol type compound (B) is a compound represented by following formula (2-1): The resin composition characterized by the above-mentioned:

(In formula (2-1), R <^14a> and R <^14b> are respectively independently a hydrogen atom or a linear or branched hydrocarbon group of 1-10 carbon atoms, R <^15> and R <^16> are each independently C1-C10 A hydrocarbon group of 10, X represents a methylene group or an alkylene group of 2 to 10 carbon atoms, Y is an n-valent group, a chain hydrocarbon group of 3 to 12 carbon atoms or a cyclic hydrocarbon group of 4 to 8 carbon atoms And n is an integer of 1 to 4). The method of claim 1,
The said phenol type compound (B) is a compound shown by following formula (2-a), The resin composition characterized by the above-mentioned.

The method of claim 1,
The said cyclic olefin resin (A) is ring-opening (co) polymerization hydrogenated body (A-2), The resin composition characterized by the above-mentioned. The method of claim 1,
Further containing phosphorus-containing compound (C) that satisfies the following requirements (Ci) and (C-ii), wherein the phosphorus-containing compound (C) is 0.005 to 5 to 100 parts by weight of cyclic olefin resin (A) Resin composition comprising a weight part:
(Ci): the relative molecular mass is 400 or more in a single compound, the weight average molecular weight (Mw) by gel permeation chromatography (GPC) in a polydisperse mixture is 400 or more,
(C-ii): The weight reduction rate at the time of 1 hour heating at 250 degreeC under nitrogen is 50% or less. The method of claim 6,
The resin composition characterized by the above-mentioned phosphorus containing compound (C) containing the structure represented by following formula (3):

(In formula (3), R <^17> and R <^18> represents a C1-C20 hydrocarbon group each independently, Ar represents an aromatic group, m represents 2 or 3, n represents 0 or 1.). The method according to claim 6 or 7,
The resin composition characterized by the above-mentioned phosphorus containing compound (C) having at least 1 sort (s) selected from the compound represented by following formula (3-a)-(3-c):

. The method of claim 5,
The resin composition, wherein the weight-average molecular weight (Mw) by gel permeation chromatography (GPC) of the ring-opening (co) polymerized hydrogenated body (A-2) is 30,000 to 200,000. The method according to claim 5 or 9,
The glass transition temperature (Tg) of the said ring-opening (co) polymerized hydrogenated body (A-2) is 100-250 degreeC, The resin composition characterized by the above-mentioned. The method according to claim 5 or 9,
The hydrogenation rate of the carbon-carbon double bond except the unsaturated bond of the aromatic ring of the said ring-opening (co) polymerization hydrogenated body (A-2) is 90% or more, The resin composition characterized by the above-mentioned. The optical component which consists of a resin composition of any one of Claims 1-7.