JP5936437B2 - Cyclic olefin resin - Google Patents

Description

  The present invention relates to a cyclic olefin resin.

  Cyclic olefin resin is a resin having a cyclic olefin skeleton in the main chain, and has high transparency, low birefringence, high heat distortion temperature, light weight, dimensional stability, low water absorption, hydrolysis resistance, chemical resistance This resin has many characteristics such as high performance, low dielectric constant, low dielectric loss, and no environmental load substances. For this reason, cyclic olefin resins are used in a wide variety of fields where these characteristics are required.

  In particular, cyclic olefin-based resins are transparent in industrial materials such as lenses, light guide plates, diffraction gratings, and other optical devices, architecture, and lighting because they can exhibit high heat resistance, high transparency, and low birefringence. It is used as a raw material for various molded products. Thus, the cyclic olefin resin may be used as a raw material for products used outdoors.

  For example, Patent Document 1 discloses an example in which a cyclic olefin-based resin is used as a raw material for products that are used outdoors for a long time. As another example used outdoors, Patent Document 2 discloses an example in which a cyclic olefin-based resin is used as a raw material for components constituting a solar cell.

JP 2004-314594 A JP 2006-198922 A

  By the way, as above-mentioned, cyclic olefin resin can be used as a raw material of an optical component, and is not a material with weak durability with respect to light. Moreover, it is as above-mentioned also about the point that cyclic olefin resin is excellent in heat resistance.

  However, although it is a cyclic olefin resin that is considered to have no problem with light resistance and heat resistance, the transparency of the cyclic olefin resin can be improved by being exposed to light for a long period of time or being exposed to a high temperature environment. May be slightly reduced by discoloration. In optical parts and the like, even a small decrease in transparency has a great influence on the quality of products.

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a cyclic olefin-based resin that hardly changes color even when exposed to light or heat for a long period of time.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, a cyclic olefin resin containing a repeating unit derived from a cyclic olefin monomer and a repeating unit derived from an acyclic olefin monomer, having a glass transition temperature of 120 ° C. or higher, and the cyclic olefin The ratio of the repeating unit derived from the monomer is 40 mol% or more and 60 mol% or less, the ratio of the repeating unit derived from the acyclic olefin monomer is 40 mol% or more and 60 mol% or less, and the cyclic olefin monomer A cyclic olefin resin in which the ratio of the meso-type double-chain site to the racemo-type double-chain site (meso-type double-chain site / racemo-type double-chain site) is 1.0 or less If it exists, it discovered that the above subject could be solved and came to complete this invention. More specifically, the present invention provides the following.

  (1) A cyclic olefin resin containing a repeating unit derived from a cyclic olefin monomer and a repeating unit derived from an acyclic olefin monomer, the glass transition temperature of which is 120 ° C. or higher, and the cyclic olefin The ratio of the repeating unit derived from the monomer is 40 mol% or more and 60 mol% or less, the ratio of the repeating unit derived from the acyclic olefin monomer is 40 mol% or more and 60 mol% or less, and the cyclic olefin monomer A cyclic olefin resin in which the ratio of the meso-type double-chain site to the racemo-type double-chain site (meso-type double-chain site / rasemo-type double-chain site) is 1.0 or less in the dimer of the repeating unit derived from

  (2) The cyclic olefin resin according to (1), wherein a ratio of the repeating unit derived from the cyclic olefin monomer in the cyclic olefin component as a trimer is 10 mol% or less.

  (3) The cyclic olefin resin according to (1) or (2), wherein an in-plane retardation at a wavelength of 520 nm on a flat plate having a thickness of 2 mm is 100 nm or less.

  (4) The difference between the yellowness (YI value) on a flat plate with a thickness of 2 mm and the yellowness (YI value) on a flat plate with a thickness of 2 mm processed at 115 ° C. for 1000 hours is 2.5 or less. The cyclic olefin resin according to any one of (1) to (3).

(5) Yellowness (YI value) of a 2 mm-thick flat plate irradiated for 500 hours in a state where light having a wavelength of 275 nm or less is blocked by a xenon lamp having an irradiation density of 162 W / m ² at a wavelength of 300 nm to 400 nm. The cyclic olefin resin according to any one of (1) to (4), wherein is 10 or less.

(6) The total light transmittance of a flat plate having a thickness of 2 mm irradiated to a xenon lamp having an irradiation density of 162 W / m ² at a wavelength of 300 nm to 400 nm for 500 hours in a state where light of a wavelength of 275 nm or less is blocked is 80. % Cyclic olefin-based resin according to any one of (1) to (5).

  (7) A cyclic olefin resin composition comprising the cyclic olefin resin according to any one of (1) to (6), an ultraviolet absorber, and a light stabilizer.

  Since the cyclic olefin-based resin of the present invention has a specific structure, even if it is exposed to light or heat for a long time, it hardly changes color.

  Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.

<Cyclic olefin resin>
The cyclic olefin resin of the present invention includes a repeating unit derived from a cyclic olefin monomer and a repeating unit derived from an acyclic olefin monomer.

  Further, the cyclic olefin resin of the present invention may be a hydrogenated product of a copolymer including a repeating unit derived from a cyclic olefin monomer and a repeating unit derived from an acyclic olefin monomer.

  The cyclic olefin-based resin of the present invention includes those obtained by grafting and / or copolymerizing an unsaturated compound having a hydrophilic group.

  Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amino group, an amide group, an ester group, a hydroxyl group, a sulfo group, a phosphono group, and a phosphino group. Saturated compounds include (meth) acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (carbon number 1 to 10) ester, alkyl maleate (carbon number 1 -10) ester, (meth) acrylamide, (meth) acrylic acid-2-hydroxyethyl and the like, preferably carboxyl group, acid anhydride group, epoxy group, amino group, amide group, ester group, A hydroxyl group, a sulfo group, a phosphono group, and a phosphino group are mentioned.

（式中、Ｒ^１〜Ｒ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、
Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、
Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。
また、ｎは、０又は正の整数を示し、
ｎが２以上の場合には、Ｒ^５〜Ｒ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。） [Repeating unit derived from cyclic olefin monomer]
The type of the repeating unit derived from the cyclic olefin monomer is not particularly limited, but is preferably a repeating unit represented by the general formula (I).

(Wherein R ^{1 to} R ¹² may be the same as or different from each other, and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group;
R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group,
R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.
N represents 0 or a positive integer;
When n is 2 or more, R ^{5 to} R ⁸ may be the same or different in each repeating unit. )

R ^{1 to} R ¹² in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

Specific examples of R ^{1 to} R ⁸ include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group. May be different from each other, may be partially different, or all may be the same.

Specific examples of R ^{9 to} R ¹² include, for example, hydrogen atom; halogen atom such as fluorine, chlorine, bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, stearyl. Alkyl group such as cyclohexyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; benzyl group, phenethyl And an aralkyl group in which an aryl group is substituted with an alkyl group, and the like. These may be different from each other, may be partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.

  Specific examples of the cyclic olefin component represented by the general formula (I) include those similar to those described in JP-A-2007-302722.

  These cyclic olefin components may be used singly or in combination of two or more. Among these, it is preferable to use bicyclo [2.2.1] hept-2-ene (common name: norbornene) alone.

  In the cyclic olefin resin of the present invention, the ratio of the repeating unit derived from the cyclic olefin monomer is 40 mol% or more and 60 mol% or less.

  The ratio of the repeating unit derived from the cyclic olefin monomer as a dimer with respect to the content of the cyclic olefin monomer is not particularly limited, but the three-dimensional structure in the dimer portion of the cyclic olefin resin of the present invention is not limited. Regarding regularity, the following conditions must be satisfied. In addition, content of a dimer is 15 mol% or more and 45 mol% or less with respect to a cyclic olefin component, for example.

It is known that the stereoregularity of the dimer includes a meso form of the following formula (II) and a racemo form of the following formula (III). In the present invention, the abundance ratio of the stereoisomer (meso type double chain site / rasemo type double chain site) is 1.0 or less. More preferably, it is 0.3 or less.

  The ratio of the repeating unit derived from the cyclic olefin monomer in the cyclic olefin component as a trimer is not particularly limited, but is preferably 10 mol% or less.

[Repeating unit derived from acyclic olefin monomer]
The kind of the repeating unit derived from the acyclic olefin monomer is not particularly limited, but is preferably a repeating unit derived from an α-olefin component having 2 to 20 carbon atoms. The α-olefin having 2 to 20 carbon atoms is not particularly limited. For example, the thing similar to Unexamined-Japanese-Patent No. 2007-302722 can be mentioned. These α-olefin components may be used alone or in combination of two or more. Of these, ethylene is most preferably used alone.

[Repeating units derived from other monomers]
The cyclic olefin-based resin of the present invention can contain a repeating unit other than the above-mentioned repeating units within a range not impairing the effects of the present invention. The unsaturated monomer that may be optionally copolymerized is not particularly limited, and examples thereof include hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule. Can be mentioned. Specific examples of the hydrocarbon-based monomer having two or more carbon-carbon double bonds in one molecule include those similar to those described in JP-A-2007-302722.

<Method for producing cyclic olefin resin>
The polymerization method and the hydrogenation method of the obtained polymer for producing the cyclic olefin resin of the present invention having the above structure are not particularly limited, and a known method can be adopted. Moreover, although random copolymerization or block copolymerization may be sufficient, it is preferable that it is random copolymerization. Moreover, the cyclic olefin resin of this invention which has the said characteristic can be manufactured by adjusting concrete manufacturing conditions. Specifically, the cyclic olefin resin of the present invention can be produced by adjusting the amount of each monomer used as a raw material, the reaction temperature, the reaction pressure, and the like according to conventionally known guidelines.

  The polymerization catalyst used is not particularly limited, and a cyclic olefin resin can be obtained by a known method using a conventionally known catalyst such as a Ziegler-Natta, metathesis, or metallocene catalyst.

  About the point which the manufactured cyclic olefin resin has the said specific structure, it can confirm by a conventionally well-known method. For example, it can be confirmed by the method described in WO2007 / 060723.

<Properties of the cyclic olefin resin of the present invention>
As above-mentioned, the cyclic olefin resin of this invention is equipped with the characteristic of (A)-(C). Furthermore, by providing the feature (D), the cyclic olefin-based resin of the present invention hardly changes color even when exposed to light or heat for a long period of time.

(A) The ratio of the repeating unit derived from a cyclic olefin-type monomer is 40 mol% or more and 60 mol% or less.
(B) The ratio of the repeating unit derived from the acyclic olefin monomer is 40 mol% or more and 60 mol% or less.
(C) In the dimer of the repeating unit derived from the cyclic olefin monomer, the ratio of the meso type double chain site to the racemo type double chain site (meso type double chain site / rasemo type double chain site) is 1.0 or less. .
(D) The glass transition temperature is 120 ° C. or higher.

  First, the effect that the product hardly discolors even when exposed to heat for a long time will be described. Since the cyclic olefin resin of the present invention has the above specific structure and has a glass transition temperature of 120 ° C. or higher, it has very high heat resistance. About glass transition temperature, it can adjust to the said range by adjusting the ratio of the repeating unit derived from the cyclic olefin type monomer in cyclic olefin type resin. Specifically, the glass transition temperature tends to increase as the number of repeating units derived from the cyclic olefin monomer increases. In the cyclic olefin resin of the present invention, a more preferable range of the glass transition temperature is 130 ° C. or higher and 170 ° C. or lower. In addition, the glass transition temperature (Tg) employ | adopts the value measured by DSC method (method of JISK7121) on the temperature increase rate of 10 degree-C / min conditions.

  Specifically, for example, the difference between the yellowness (YI value) on a flat plate with a thickness of 2 mm and the yellowness (YI value) on a flat plate with a thickness of 2 mm processed under the conditions of 115 ° C. and 1000 hours is 2 .5 or less. About a flat plate, the flat plate of thickness 2mm manufactured by the method as described in the Example mentioned later is used.

  Next, the effect that the product hardly discolors even when exposed to light for a long time will be described. Since the cyclic olefin resin of the present invention has a specific structure as described above, it has very high light resistance.

Specifically, the yellowness (YI) of a flat plate having a thickness of 2 mm irradiated with a xenon lamp having an irradiation density of 162 W / m ² at a wavelength of 300 nm to 400 nm for 500 hours in a state where light of a wavelength of 275 nm or less is blocked. Value) is 10 or less. Further, the total light transmittance of a 2 mm-thick flat plate irradiated with a xenon lamp having a wavelength of 300 nm to 400 nm and having an irradiation density of 162 W / m ² in a state where light having a wavelength of 275 nm or less is blocked is 80%. That's it.

  The cyclic olefin-based resin of the present invention having excellent light resistance and heat resistance as described above has a small phase difference due to the specific structure described above. Specifically, the in-plane retardation at a wavelength of 520 nm on a flat plate having a thickness of 2 mm is 100 nm or less. A specific method of measuring the phase difference is as described in the examples.

  The cyclic olefin resin of the present invention having the above properties is suitable as a raw material for parts used outdoors or parts used in a high temperature environment. For example, the cyclic olefin resin of the present invention can be suitably used as a raw material for LED lenses and vehicle-mounted lenses.

  In addition, when manufacturing a product using the cyclic olefin resin of this invention, it is good also considering the cyclic olefin resin composition containing the cyclic olefin resin of this invention and another component as a raw material. Examples of other components include other types of thermoplastic resins and additives such as reinforcing agents, plasticizers, stabilizers, and pigments.

  In the present invention, it is preferable to use a stabilizer in combination. As the stabilizer, it is preferable to use an ultraviolet absorber, a light stabilizer, or an antioxidant. Use of these stabilizers further enhances the effect of improving heat resistance and light resistance.

  Examples of the UV absorber include benzotriazole UV absorbers, triazine UV absorbers, benzophenone UV absorbers, and malonic ester UV absorbers.

  Specifically, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2- (2H-benzotriazol-2-yl) -4 -6-bis (1-methyl-1-phenylmethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2,2 ' -Methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) Enol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2 '-Hydroxy-3', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotri Sol, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl)] benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5) '', 6 ''-tetrahydrophthaloid-methyl) -5'-methylphenyl] -benzotriazole, 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N -Benzotriazol-2-yl) phenol], methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300) Condensates of: phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate Hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 (Octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5 -Triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol, tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate, 2,2 ' -Thiobis (4-t-octylphenol) Ni salt, [2,2'-thiobis (4-t-octylphenolate)]-n-butylamine Ni salt, (3,5-di-t-butyl-4-hydroxy) Cibenzyl) phosphonic acid monoethyl ester Ni salt, (3,5-di-t-butyl-4-hydroxybenzyl) phosphonic acid monooctyl ester Ni salt, dibutyldithiocarbamate Ni salt, α-cyano-β-methyl-β ( p-methoxyphenyl) methyl acrylate, methyl α-cyano-β, β-diphenyl acrylate, N-2-ethylphenyl-N′-2-ethoxy-5-t-phenyloxalic acid diamide, N-2-ethylphenyl -N'-2-ethoxyphenyl oxalate is mentioned. Among these, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol, 2- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol, 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine- 2-yl] -5- (octyloxy) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- (4,6 -Diphenyl 1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol, tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate Is preferred.

  Although content of a ultraviolet absorber is not specifically limited, It is preferable that it is 0.01 to 0.5 mass% in a cyclic olefin resin composition, and is 0.05 to 0.2 mass%. More preferably.

  Examples of the light stabilizer include hindered amine light stabilizers and benzoate light stabilizers.

  Specifically, 2,2,6,6-tetramethyl-4-piperidine stearin, probandioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) ester, 1,6 hexadiamine-N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl) -morpholine-2,4,6-trichloro-1,3,5- Triazine reactant, bis (2,2 ′, 6,6′-tetramethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-succinate Tetramethylpiperidine polycondensate, poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6 -Tetramethyl-4 Piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3 4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di- t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) ) -4-Hydroxyphenyl] methyl} butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 ′-(1,2-ethanediyl) Screw( , 3,5,5-tetramethylpiperazinone), (mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed {2,2,6,6-tetramethyl-4-piperidyl / Β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetra Carboxylate, mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxa Spiro (5,5) undecane] } -1,2,3,4-butanetetracarboxylate, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6, 6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2 , 2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6 , 6-Tetramethyl-4-piperidyl) hexamethylenediamine and 1,2-dibromoethane condensate, [N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl-2 -(2,2,6,6-tetramethyl-4-pi Peridyl) imino] propionamide, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate, 2,6-di-t-butylphenyl-3 ′, 5'-di-t-butyl-4'-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate and n-octadecyl-3,5-di-t-butyl-4- Examples thereof include hydroxybenzoate. Among these, 2,2,6,6-tetramethyl-4-piperidine stearin, probandioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4- Piperidyl) ester, 1,6 hexadiamine-N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl) -morpholine-2,4,6-trichloro-1,3,5-triazine Preference is given to using the reactants, bis (2,2 ′, 6,6′-tetramethyl-4-piperidyl) sebacate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate.

  Although content of a light stabilizer is not specifically limited, It is preferable that it is 0.05 to 1 mass% in a cyclic olefin resin composition, and it is 0.2 to 0.4 mass%. Is more preferable.

Examples of the antioxidant include hindered phenol antioxidants and phosphorus antioxidants. As a hindered phenol antioxidant, a polycyclic ring connected by a monocyclic hindered phenol compound (for example, 2,6-di-t-butyl-p-cresol etc.), a hydrocarbon group or a group containing a sulfur atom Hindered phenol compounds of the formula (for example, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 4,4'-thiobis (3-methyl-6-tert-butylphenol)), ester group or A hindered phenol compound having an amide group (for example, n-octadecyl-3- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, n-octadecyl-2- (4′-hydroxy-) 3 ′, 5′-di-t-butylphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3.9 -Bis {2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl -2,4,8,10-tetraoxaspiro [5.5] undecane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methyl Phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, di-n-octadecyl-3,5-di -T-butyl-4-hydroxybenzylphosphonate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-dihydrocinnamamide, N, N'-ethylenebis [3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionamide], N, N′-tetramethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionamide], N N′-hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], N, N′-ethylenebis [3- (3-tert-butyl-5-methyl-) 4-hydroxyphenyl) propionamide], N, N′-hexamethylenebis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionamide], N, N′-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionyl]
Hydrazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl) isocyanurate and the like.

  Specific examples of phosphorus antioxidants include tris (2,4-tert-butylphenyl) phosphite, bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester Phosphoric acid, tetrakis (2,4-di-t-butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphonite, bis (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol-diphosphite, tetrakis (2,4-t- Butylphenyl) (1,1-biphenyl) -4,4′-diylbisphosphonite, di-t-butyl-m-cresyl-phosphonite, etc. It is. Of these, the use of tris (2,4-tert-butylphenyl) phosphite is preferred.

  Although content of a stabilizer is not specifically limited, It is preferable that it is 0.05 mass% or more and 1.0 mass% or less in the cyclic olefin resin composition containing cyclic olefin resin and the said stabilizer. If it is 0.05% by mass or more, it is preferable because the initial optical characteristics of the molded product are high, and sufficient heat resistance and light discoloration are exhibited. If it is 1.0% by mass or less, the initial optical characteristics of the molded product are preferable. It is preferable because it does not impair. A more preferable content is 0.1% by mass or more and 0.5% by mass or less.

<Method for Producing Cyclic Olefin Resin Composition>
The manufacturing method of the cyclic olefin resin composition of this invention is not specifically limited. In general, a resin composition can be prepared by a known equipment and method as a method for preparing a resin composition. For example, necessary components can be mixed and kneaded using a single or twin screw extruder or other melt kneader to prepare pellets for molding. All components may be charged simultaneously from the hopper and melt kneaded, or some components may be charged from the side feed port and melt kneaded. In addition, when a master batch pellet containing a high concentration of a stabilizer in a cyclic olefin resin is prepared using a melt kneader and a resin molded body as described later is produced, the cyclic olefin does not contain the stabilizer. The product may be molded by mixing the buster batch pellets with the resin pellets so that the desired concentration (stabilizer concentration) is obtained. Further, when a resin molded body as described later is manufactured without manufacturing a molding pellet as described above, a product may be molded by directly covering a cyclic olefin resin pellet with a stabilizer.

<Production method of resin molding>
The resin molded body can be manufactured by a conventionally known molding method. Conventionally known molding methods include molding methods such as injection molding and extrusion molding.

<Resin molding>
The cyclic olefin resin composition of the present invention includes an in-vehicle optical lens that requires light heat resistance, a lens or a reflector of an illumination device that uses an LED, a cold cathode tube, or the like that requires heat resistance and light resistance at the same time, It can be preferably used as a raw material for parts constituting a solar cell. For optical components that require transparency, transparency degradation is a problem due to resin degradation due to exposure to high-temperature environments, LED light sources, cold cathode tube light sources themselves, and external light. This is because the transparency can be maintained in a high state even when exposed to light or heat for a long period of time.

  Hereinafter, the present invention will be described with reference to examples and comparative examples. The present invention is not limited to the following examples.

<Synthesis of Cyclic Olefin Resin 1>
Synthesis of the cyclic olefin-based resin 1 was carried out by adding norbornene, a hydrocarbon solvent (polymerization solvent), ethylene, and hydrogen to a continuous polymerization apparatus, a norbornene supply amount of 81 kg / h, a polymerization solvent supply amount of 19 kg / h, The supply amount of ethylene was 4.5 kg / h, and the supply amount of hydrogen was 0.64 g / h. At the same time, a catalyst system comprising diphenylmethylidene-cyclopentadienylfluorenylzirconium dichloride as a catalyst (polymerization catalyst) and methylalumoxane (10% toluene solution) as a co-catalyst was supplied to the reactor. In the subsequent desolvation step, the temperature of the reaction apparatus is kept at 70 ° C., and 0.1% of an antioxidant (trade name, Irganox 1010, manufactured by BASF) is added to the cyclic olefin resin in the stirring tank of the next step. The solvent was removed under high temperature and reduced pressure. The copolymer in a molten state was extruded into a strand shape and cut into pellets.

<Synthesis of Cyclic Olefin Resin 2>
The synthesis of the cyclic olefin resin 2 was carried out by adding norbornene, a hydrocarbon solvent (polymerization solvent), ethylene, and hydrogen in a continuous polymerization apparatus, a norbornene supply amount of 52 kg / h, a polymerization solvent supply amount of 23 kg / h, The supply amount of ethylene was 4.0 kg / h, and the supply amount of hydrogen was 0.67 g / h. At the same time, a catalyst system comprising diphenylmethylidene-cyclopentadienylfluorenylzirconium dichloride as a catalyst (polymerization catalyst) and methylalumoxane (10% toluene solution) as a co-catalyst was supplied to the reactor. In the subsequent desolvation step, the temperature of the reaction apparatus is kept at 70 ° C., and 0.1% of an antioxidant (trade name, Irganox 1010, manufactured by BASF) is added to the cyclic olefin resin in the stirring tank of the next step. The solvent was removed under high temperature and reduced pressure. The copolymer in a molten state was extruded into a strand shape and cut into pellets.

<Synthesis of Cyclic Olefin Resin 3>
The synthesis of the cyclic olefin-based resin 3 was carried out by mixing norbornene, a hydrocarbon solvent (polymerization solvent), ethylene, and hydrogen in a continuous polymerization apparatus, a norbornene supply amount of 44 kg / h, a polymerization solvent supply amount of 23 kg / h, The supply amount of ethylene was 2.8 kg / h, and the supply amount of hydrogen was 0.3 g / h. At the same time, a catalyst system comprising diphenylmethylidene-cyclopentadienylindenylzirconium dichloride as a catalyst (polymerization catalyst) and methylalumoxane (10% toluene solution) as a co-catalyst was supplied to the reactor. In the subsequent desolvation step, the temperature of the reaction apparatus is kept at 70 ° C., and 0.1% of an antioxidant (trade name, Irganox 1010, manufactured by BASF) is added to the cyclic olefin resin in the stirring tank of the next step. The solvent was removed under high temperature and reduced pressure. The copolymer in a molten state was extruded into a strand shape and cut into pellets.

<Synthesis of Cyclic Olefin Resin 4>
The synthesis of the cyclic olefin-based resin 4 was conducted by adding norbornene, a hydrocarbon solvent (polymerization solvent), ethylene, and hydrogen to a continuous polymerization apparatus, a norbornene supply amount of 28 kg / h, a polymerization solvent supply amount of 22 kg / h, Ethylene was supplied at a rate of 3.0 kg / h, and hydrogen was supplied at a rate of 0.18 g / h. At the same time, a catalyst system comprising diphenylmethylidene-cyclopentadienylindenylzirconium dichloride as a catalyst (polymerization catalyst) and methylalumoxane (10% toluene solution) as a co-catalyst was supplied to the reactor. In the subsequent desolvation step, the temperature of the reaction apparatus is kept at 70 ° C., and 0.1% of an antioxidant (trade name, Irganox 1010, manufactured by BASF) is added to the cyclic olefin resin in the stirring tank of the next step. The solvent was removed under high temperature and reduced pressure. The copolymer in a molten state was extruded into a strand shape and cut into pellets.

<Evaluation of materials>
For cyclic olefin-based resin 1 to cyclic olefin-based resin 4, the proportion of repeating units derived from the cyclic olefin-based monomer, the proportion of repeating units derived from the cyclic olefin-based monomer in the cyclic olefin-based component, 3 Ratio existing as a mer, ratio of meso-type double-linked site and racemo-type double-linked site (meso-type double-linked site / rasemo-type double-linked site (meso-racemo ratio)), acyclic The ratio of the repeating unit derived from the olefin monomer was determined by the following method.

  Ratio of chain olefin monomer (acyclic olefin monomer) and bridged cycloalkene monomer (norbornene monomer), doublet site (dimer), triple The child site (trimer) and the meso-racemo ratio can be calculated from the integral value of the spectrum observed by 13C-NMR.

  The primary structure of the polymer identified by each spectrum is “Macromol. Chem. Phs. 1999, Vol. 200, Page 1340”, “Macromolecules 2004, Vol. 37, Page 9681”, “Macromolecules 2000, Vol. 33,”. Page 8931 "and the like.

  A specific parameter calculation method when the chain olefin monomer is ethylene and the bridged cycloalkene monomer (norbornene monomer) is norbornene will be described.

First, the calculation of the composition will be described. The composition is an integral value observed at a chemical shift value of 44.5-56.0 ppm in the spectrum chart obtained by 13C-NMR: IC2, C3 (derived from the 2nd and 3rd positions of the norbornene ring),
Integral values observed at a chemical shift value of 37.0-44.0 ppm: IC1, C4 (derived from carbons at positions 1 and 4 of the norbornene ring),
Integral value observed at a chemical shift value of 36.5-33.0 ppm: IC7 (derived from the 7th carbon of the norbornene ring),
Integral observed at a chemical shift value of 44.5-56.0 ppm: From IC5, C6 + IE (derived from the carbons at the 5th and 6th positions of the norbornene ring and the carbon of the ethylene part), derived from the cyclic olefin monomer from the following formula: The ratio of repeating units to be obtained (composition of the norbornene component) can be determined. Further, by subtracting the composition of the norbornene component from 100%, the ratio of the repeating unit derived from the acyclic olefin monomer can be calculated.

  The ratio of the amount of the doublet site (NN dyad in the formula) and the triplet site (NN triad in the formula) is described in “Macromol. Chem. Phs. 1999, Vol. 200, Page 1340”. The distribution of six triads (EEE, EEN, NEN, NNN, NNE, ENE) can be obtained and calculated from the following equation.

  The mole fraction of the NN dyad meso form is the integral of the C5 ENNE-meso peak (28.0-28.5 ppm) and the C6 ENNE-meso peak (31.5-31.8 ppm). And the integrated value of the C7, EN6-meso peak (33.1-33.2 ppm) of the C7, C6, ethylene portion region (29.4-32.5 ppm) and the C7 ENNE-meso peak. It is determined from the average value of the composition of norbornene and the value divided by the integrated value of the C7 region (32.6-39 ppm).

  Similarly, the mole fraction of the racemo body of the NN dyad is the integrated value of the C5 ENNE-racemo peak (28.0-28.5 ppm) and the C6 ENNE-rasemo peak (31.2-31.31). 4 ppm) divided by the peak (28-32.5 ppm) in the region of C5, C6, and ethylene, and the integrated value of the C7 ENNE-Racemo peak (33.4-33.8 ppm) is norbornene And the average value of the value divided by the integral value of the C7 region (32.6-39 ppm).

An example of sample preparation conditions and measurement conditions in the present invention is as follows.
Solvent: 1,1,2,2-tetrachloroethane-d2 (containing 10% by volume of hexamethyldisilane)
Concentration: 70 mg / mL
Apparatus: Bruker AVANCE 600 (resonance frequency of hydrogen atom: 600 MHz)
Sample tube diameter: 10 mm
Measuring method: Power gate type pulse width: 15μsec
Delay time: 2.089sec
Data acquisition time: 0.911 sec
Observation frequency width: 35971.22Hz
Decoupling: Total number of complete decoupling: 18000 times Chemical shift reference: Hexamethyldisilane peak is -2.43 ppm.

Table 1 shows the structure of the cyclic olefin resin obtained by the above measurement, the glass transition temperature (Tg) and MVR of the cyclic olefin resin. The MVR was measured based on ISO 1133, and the volume of the resin discharged in 10 minutes at a temperature of 260 ° C. and a load of 2.16 kg (mL / 10 minutes) was determined. As Tg, a value measured by a DSC method (method described in JIS K7121) under a temperature rising rate of 10 ° C./min was adopted.

<Preparation of test piece for evaluation>
Using a Sumitomo Heavy Industries injection molding machine SE75D, a flat plate of 70 × 70 × thickness 2 mmt was manufactured under the conditions of a cylinder temperature of Tg + 140 ° C. and an injection speed of 150 mm / sec. This flat plate was used for the retardation evaluation, heat resistance evaluation, and light resistance evaluation described below. In the following evaluation, polycarbonate resin 1 (Iupilon (registered trademark) ML-300 (manufactured by Mitsubishi Engineering Plastics)), polycarbonate resin 2 (Panlite (registered trademark) L-1225ZL100 (manufactured by Teijin Chemicals Ltd.)) ) Was molded into the same shape as the above test piece, and these were also evaluated.

[Evaluation of phase difference]
The in-plane retardation at a wavelength of 520 nm at the center of the surface of the plate-shaped test piece was measured using a two-dimensional birefringence evaluation apparatus (PA-100 (manufactured by Photonic Lattice)). The measurement results are shown in Table 2.

  From the result of Table 2, it was confirmed that the molded object comprised from the cyclic olefin resin of this invention has a small phase difference.

[Heat-resistant]
First, yellowness (YI) was measured for each test piece after molding. Specifically, yellowness (DIN 6167) was measured with a color difference meter color-sphere manufactured by YKB-Gardnar GmbH. Subsequently, each test piece was heat-treated at 115 ° C. for 1000 hours, and the yellowness was measured after the heat treatment. Furthermore, the difference in yellowness before and after heat treatment was calculated. Table 3 shows the difference in yellowness before heat treatment, yellowness after heat treatment, and yellowness.

  From the results shown in Table 3, it was confirmed that the cyclic olefin-based resin of the present invention hardly discolored even when exposed to a high temperature environment for a long time.

[Light resistance]
First, yellowness (YI) was measured for each test piece after molding. Next, each test piece was irradiated with light for 500 hours, and the yellowness was measured after the light irradiation. The difference in yellowness before and after light irradiation was calculated. The results are shown in Table 4. Here, light irradiation uses a Suga test machine super xenon weather meter, filter # 275 (cutting 275 nm or less), black panel temperature 89 ° C., humidity 50% RH, irradiation density 162 W / m ² (300 to 400 nm), The total energy amount was 291.5 MJ / m ² .

Further, the total light transmittance before and after the light irradiation was measured. Specifically, the total light transmittance was measured by a method based on JIS K7136 using a haze meter (manufactured by Toyo Seiki Seisakusho, trade name: Hazeguard II). The results are shown in Table 4.

  It was confirmed that the cyclic olefin-based resin of the present invention hardly discolored even when exposed to light for a long period of time, and the decrease in light transmittance was small.

<Evaluation example of cyclic olefin resin composition>
A test piece for evaluation was prepared in the same manner as described above except that the cyclic olefin resin composition containing the cyclic olefin resin 1 and the ultraviolet absorbent, light stabilizer, and antioxidant shown in Table 5 below was used as a raw material. The heat resistance and light resistance were evaluated.

[Stabilizer]
Ultraviolet absorber 1: 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylmethyl) phenol (Tinuvin 234, manufactured by BASF Japan Ltd.)
Ultraviolet absorber 2: 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (Tinuvin 329, manufactured by BASF Japan Ltd.)
Ultraviolet absorber 3: 2,2′-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (LA-31, ADEKA Corporation) Made)
Ultraviolet absorber 4: 2- (2H-benzotriazol-2-yl) -4,6-di-tert-pentylphenol (Tinuvin 328, manufactured by BASF Japan Ltd.)
UV absorber 5: 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol (CYASORB UV-1164, CYTEC INDUSTRIES) Made)
Ultraviolet absorber 6: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (Tinvin 1577, manufactured by BASF Japan Ltd.)
Ultraviolet absorber 7: 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] -phenol (LA-46, Inc. Made by ADEKA)
Ultraviolet absorber 8: tetra-ethyl-2,2- (1,4-phenylene-dimethylidene) -bismalonate (Hostavin B-CAP, manufactured by Clariant Japan)
Light stabilizer 1: 2,2,6,6-tetramethyl-4-piperidine stearin (CYASORB UV-3853, manufactured by CYTEC INDUSTRIES)
Light stabilizer 2: bis (2,2 ′, 6,6′-tetramethyl-4-piperidyl) sebacate (Tinuvin 770, manufactured by BASF Japan Ltd.)
Light stabilizer 3: Probandioic acid [{4-methoxyphenyl} methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester (Hostavin PR-31, manufactured by Clariant Japan)
Light Stabilizer 4: 1,6 Hexadiamine-N, N-bis (2,2,6,6-tetramethyl-4-piperidinyl) -morpholine-2,4,6-trichloro-1,3,5- Triazine reactant (CYASORB UV-3529, manufactured by CYTEC INDUSTRIES)
Light stabilizer 5: n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate (CYASORB UV-2908, manufactured by CYTEC INDUSTRIES)
Antioxidant: Tris (2,4-tert-butylphenyl) phosphite (Irgafos168, manufactured by BASF Japan Ltd.)
Mixture 1: Mixture of UV absorber and light stabilizer (light stabilizer 1) (CYASORB 7001EF, manufactured by CYTEC INDUSTRIES)
Mixture 2: Mixture of UV absorber (UV absorber 5) and light stabilizer (light stabilizer 4) (CYASORB THT6435, manufactured by CYTEC INDUSTRIES)

[Heat-resistant]
About each test piece after shaping | molding, it showed in Table 6 about the yellowness before heat processing measured by the method similar to the above, the yellowness after heat processing, and the difference in yellowness. The evaluation results of Example 1 are also shown in Table 1.

[Light resistance]
About each test piece after shaping | molding, it showed in Table 6 about the difference of the yellowness (YI) before irradiation, the yellowness (YI) after irradiation, and the yellowness (YI) measured by the method similar to the above. Table 6 shows the total light transmittance before irradiation and the total light transmittance after irradiation, measured by the same method as described above. The evaluation results of Example 1 are also shown in Table 1.

  From Table 6, it was confirmed that heat resistance and light resistance were improved by using a cyclic olefin resin composition containing an ultraviolet absorber and a light stabilizer, as compared with the results of the cyclic olefin resin.

Claims (7)

A cyclic olefin resin comprising a repeating unit derived from a cyclic olefin monomer and a repeating unit derived from an acyclic olefin monomer,
The glass transition temperature is 120 ° C. or higher,
The proportion of repeating units derived from the cyclic olefin monomer is 40 mol% or more and 60 mol% or less,
The proportion of repeating units derived from the acyclic olefin-based monomer is 40 mol% or more and 60 mol% or less,
In the dimer of repeating units derived from the cyclic olefin monomer, the ratio of the meso-type double-chain site to the racemo-type double-chain site (meso-type double-chain site / rasemo-type double-chain site) is 1.0 or less. The
The proportion of the dimer of repeating units derived from the cyclic olefin monomer is 15 mol% or more and 29 mol% or less with respect to the cyclic olefin component,
The ratio of the trimer of the repeating unit derived from the said cyclic olefin type monomer is cyclic olefin type resin which is 10 mol% or less with respect to the said cyclic olefin type component .   2. The cyclic olefin resin according to claim 1, wherein a ratio of the repeating unit derived from the cyclic olefin monomer as a trimer in the cyclic olefin component is 10 mol% or less.   The cyclic olefin resin according to claim 1 or 2, wherein an in-plane retardation at a wavelength of 520 nm on a flat plate having a thickness of 2 mm is 100 nm or less.   The difference between the yellowness (YI value) of a flat plate having a thickness of 2 mm and the yellowness (YI value) of a flat plate having a thickness of 2 mm processed under conditions of 115 ° C. and 1000 hours is 2.5 or less. The cyclic olefin resin according to any one of 1 to 3. Yellowness (YI value) on a 2 mm thick flat plate irradiated for 500 hours in a state where light having a wavelength of 275 nm or less is blocked by a xenon lamp having an irradiation density of 162 W / m ² at a wavelength of 300 nm to 400 nm is 10 or less. The cyclic olefin-based resin according to any one of claims 1 to 4. When the xenon lamp having an irradiation density of 162 W / m ² at a wavelength of 300 nm to 400 nm is irradiated for 500 hours in a state where light of a wavelength of 275 nm or less is blocked, the total light transmittance is 80% or more. The cyclic olefin resin according to any one of claims 1 to 5.   The cyclic olefin resin composition containing the cyclic olefin resin in any one of Claim 1 to 6, an ultraviolet absorber, and a light stabilizer.