JP2000186189A - Light guiding element made of norbornene-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light guiding element excellent in transparency and heat resistance and also to provide a light guiding element where the absorption loss of introduced light is small. SOLUTION: This light guiding element is produced by molding a molding material including (A) a norbornene-based polymer and (B) a phenol-based antioxidant having at least one structural unit of the formula [wherein, R1 is H, a lower alkyl or an aryl; R2 is H or a lower alkyl; (n) is 1 or 2]. It is preferable that the norbornene-based polymer includes at least repeating units not having norbornene structure, the optical path length of the light guiding element is >=100 mm and the light guiding element is a light guiding plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light guide having excellent transparency and heat resistance, and further to a light guide having a small absorption loss of introduced light.

[0002]

2. Description of the Related Art Norbornene polymers have excellent properties such as transparency, heat resistance, mechanical toughness, and low water absorption. For example, optical disks, optical fibers, optical cards, optical lenses, Fresnel lenses, Lenticular lenses, optical mirrors, liquid crystal display element substrates, light guide plates, light diffusion plates, polarizing films, retardation films, light diffusion sheets, prism sheets, condensing sheets, automotive window and roof materials, aircraft window materials, automatic It has begun to be used in a wide range of fields such as window materials for vending machines, show window materials, and showcase materials. BACKGROUND ART Conventionally, an antioxidant is added to a norbornene-based polymer for the purpose of suppressing or preventing deterioration due to oxidative degradation due to oxygen in the air and deterioration in production and use. As the antioxidants, phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants and the like are used.

In the field of optical materials, for example, for light guides represented by light guide plates, the size of products is increasing, and the need for light guides having a long optical path length is also increasing. Higher light transmission is required. However, when an antioxidant is blended with a norbornene-based polymer, there is a problem that light transmittance decreases with an increase in the blending amount. Conversely, when the blending amount is reduced, coloring due to insufficient heat resistance during melt molding occurs. In addition, there has been a problem that the molded product is burnt due to this.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light guide excellent in transparency and heat resistance, and furthermore, a light guide having a small absorption loss of introduced light.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the decrease in light transmittance due to the compounding amount of the antioxidant is due to the light absorption property of the antioxidant itself. When a light guide made of a molding material in which a specific antioxidant is blended with a norbornene-based polymer has a low light absorbing property of the antioxidant itself, and when the molding material is melt-molded, It has been found that yellowing is less likely to occur, and that the colorant has excellent coloring resistance, and that sufficient performance can be obtained even when the optical path length of the light guide is long.

The present inventors have also proposed a combination of a norbornene-based polymer containing at least 10% by weight of a repeating unit having no norbornane structure in the norbornene-based polymer and the above-mentioned specific antioxidant. It has been found that light resistance is improved by using the molded article, and that light transmittance can be maintained for a long period of time using the molded article. The present invention has been completed based on these findings.

[0007]

According to the present invention, 100 parts by weight of a norbornene-based polymer is represented by the general formula (1):

[0008]

Embedded image

(In the formula, R ¹ represents hydrogen or a lower alkyl group or an aryl group. R ² represents a hydrogen or lower alkyl group, and n represents an integer of 1 or 2.)

And a phenolic antioxidant having at least one structural unit represented by the formula:

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Norbornene-based polymer The norbornene-based polymer used in the present invention is not particularly limited, and is disclosed in, for example, JP-A-3-14882 and JP-A-3-122137. It is a known polymer disclosed, specifically, a ring-opened polymer of a norbornene-based monomer or a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and a polymer having another monomer copolymerizable with the norbornene-based monomer. And a polymer. Among these, a ring-opened polymer of a norbornene-based monomer, or a hydrogenated product thereof is preferable, and a ring-opened polymer of a norbornene-based monomer, in order to highly balance properties such as transparency, mechanical strength, and heat resistance. Is particularly preferred.

In the present invention, transparency, light fastness,
In order to achieve a high balance between light transmittance and light transmittance, a norbornene-based polymer having at least a repeating unit having no norbornane structure is preferable. The proportion of the repeating unit having no norbornane structure in the norbornene-based polymer is
It is usually at least 10% by weight, preferably at least 20% by weight, more preferably at least 30% by weight, and the upper limit is 100% by weight. When the proportion of the unit in the norbornene-based polymer is within the above range, the light resistance and the optical transparency of the light guide having a long optical path are highly balanced, which is preferable.

Examples of the norbornene-based polymer having at least a repeating unit having no norbornane structure include a ring-opened polymer of a norbornene-based monomer containing a norbornene-based monomer having no norbornane structure and a hydrogenated product thereof. And their hydrogenated products are particularly preferred. Note that the norbornane structure refers to a structure having a norbornane ring skeleton, does not have a carbon-carbon double bond, and has a norbornene ring skeleton that is opened by ring-opening polymerization (carbon-carbon that is cleaved by ring-opening polymerization). (Having a double bond) (norbornene structure).

Examples of norbornene monomers having no norbornane structure include bicyclo [2,2,1]-
Hept-2-ene (common name: norbornene), 5-methyl-bicyclo [2,2,1] -hept-2-ene, 5,
5-dimethyl-bicyclo [2,2,1] -hept-2-
Ene, 5-ethyl-bicyclo [2,2,1] -hept-
2-ene, 5-butyl-bicyclo [2,2,1] -hept-2-ene, 5-hexyl-bicyclo [2,2,1]
-Hept-2-ene, 5-octyl-bicyclo [2,
2,1] -hept-2-ene, 5-octadecyl-bicyclo [2,2,1] -hept-2-ene, 5-ethylidene-bicyclo [2,2,1] -hept-2-ene, 5 −
Methylidene-bicyclo [2,2,1] -hept-2-ene, 5-vinyl-bicyclo [2,2,1] -hept-2
-Ene, 5-propenyl-bicyclo [2,2,1] -hept-2-ene, 5-methoxy-carbonyl-bicyclo [2,2,1] -hept-2-ene, 5-cyano-bicyclo [2 , 2,1] -Hept-2-ene, 5-methyl-
5-methoxycarbonyl-bicyclo [2,2,1] -hept-2-ene, 5-methoxycarbonyl-bicyclo [2,2,1] -hept-2-ene, 5-ethoxycarbonyl-bicyclo [2,2 , 1] -Hept-2-ene,
5-methyl-5-ethoxycarbonyl-bicyclo [2,
2,1] -hept-2-ene,

Bicyclo [2,2,1] -hept-5-enyl-2-methylpropionate, bicyclo [2,2,1
1] -hept-5-enyl-2-methyloctanoate,
Bicyclo [2,2,1] -hept-2-ene-5,6-
Dicarboxylic anhydride, 5-hydroxymethyl-bicyclo [2,2,1] -hept-2-ene, 5,6-di (hydroxymethyl) -bicyclo [2,2,1] -hept-2
-Ene, 5-hydroxy-i-propyl-bicyclo [2,2,1] -hept-2-ene, bicyclo [2,
2,1] -Hept-2-ene, 5,6-dicarboxy-
Bicyclo [2,2,1] -hept-2-ene, bicyclo [2,2,1] -hept-2-ene-5,6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2,2,
1] -hept-2-ene, 5-cyclohexyl-bicyclo [2,2,1] -hept-2-ene, 5-cyclohexenyl-bicyclo [2,2,1] -hept-2-ene,
5-phenyl-bicyclo [2,2,1] -hept-2-
En,

Tricyclo [4,3,1 ^2,5 ,
0 ^1,6] - dec-3,7-diene (common name dicyclopentadiene), tricyclo ^{[4,3,1 2,5,} 0
^1,6 ] -dec-3-ene, tricyclo [4,4,1
^{2,5, 0 1,6]} - undec-3,7-diene, tricyclo ^{[4,4,1 2,5, 0 1,6]} - undec -
3,8-diene, tricyclo ^{[4,4,1 2,5,} 0
^1,6 ] -undec-3-ene, tetracyclo [7,
4,1 ^{10, 13, 0 1,9, 0 2,7]} - trideca -
2,4,6-11-tetraene (1,4-methano-1,
4,4a, 9a-tetrahydrofluorene),
Tetracyclo ^[8,4,1 11, ^{14, 0 1, 10,} 0
^3,8 ] -tetradeca-3,5,7,12-11-tetraene (1,4-methano-1,4,4a, 5,10,1
0a-hexahydroanthracene).

These norbornene monomers having no norbornane structure can be used alone or in combination of two or more. When a norbornene-based monomer having no norbornane structure is subjected to ring-opening polymerization, it becomes a repeating unit having no norbornane structure.

The rest of the norbornene-based polymer other than the repeating unit having no norbornane structure is not particularly limited, but is usually a repeating unit having a norbornane structure. The repeating unit having a norbornane structure is a ring-opened polymer of a norbornene-based monomer and, in the case of a hydrogenated product thereof, a unit obtained by ring-opening polymerization of a norbornene-based monomer having at least one norbornane structure.

Examples of the norbornene-based monomer having at least one norbornane structure include tetracyclo [4,
4,1 ^{2,5, 1 7,10,} 0] - (also referred to simply as tetracyclododecene) dodeca-3-ene, 8-methyl -
Tetracyclo ^{[4,4,1 2, 5, 1 7,10,} 0] -
Dodeca-3-ene, 8-methyl-tetracyclo [4,
4,1 ^{2,5, 1 7,10,} 0] - dodeca-3-ene,
8-ethyl - tetracyclo ^{[4,4,1 2,5,} 1
^7,10,0 ] -Dodeca-3-ene, 8-methylidene-
Tetracyclo ^{[4,4,1 2,5, 1 7,10,} 0] -
Dodeca-3-ene, 8-ethylidene - tetracyclo ^{[4,4,1 2,5, 1 7,10,} 0] - dodeca-3
Ene, 8-vinyl - tetracyclo ^{[4,4,1 2,5,}
1 ^7,10, 0] - dodeca-3-ene, 8-propenyl - tetracyclo ^{[4,4,1 2,5, 1 7,1} 0, 0]
-Dodeca-3-ene,

[0020] 8-methoxycarbonyloxy - tetracyclo ^{[4,4,1 2,5, 1 7,10,} 0] - dodeca-3
Ene, 8-methyl-8-methoxycarbonyl - tetracyclo ^{[4,4,1 2,5, 1 7,10,} 0] - dodeca -
3-ene, 8-hydroxymethyl-tetracyclo [4,
4,1 ^{2,5, 1 7,10,} 0] - dodeca-3-ene,
8-carboxy - tetracyclo ^{[4,4,1 2,5,} 1
^7,10, 0] - dodeca-3-ene, 8-cyclopentyl-- tetracyclo ^{[4,4,1 2,5, 1 7,10,}
0] - dodeca-3-ene, 8-cyclohexyl - tetracyclo ^{[4,4,1 2, 5, 1 7,10,} 0] - dodeca-3-ene, 8-cyclohexenyl - tetracyclo [4,4,1 ^{2,5, 1 7,10,} 0] - dodeca-3
Ene, 8-phenyl-tetracyclo [4,4,
1 ^{2,5, 1 7,10,} 0] - dodeca-3-ene, pentacyclo ^{[6,5,1 1,8,} 1 ^{3,6, 0 2,7,} 0
^{9, 13]} - pentadeca-3,10-diene, pentacyclo ^{[7,4,1 3,6, 1} 10, ^{13, 0 1,} 9, 0
^2,7 ] -pentadeca-4,11-diene and the like. These norbornene monomers having one or more norbornane structures can be used alone or in combination of two or more.

The ring-opening polymerization of the norbornene-based monomer can be carried out in the usual manner in the presence of a ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst include, for example, ruthenium, rhodium, palladium, osmium, iridium, a metal halide such as platinum, a nitrate or an acetylacetone compound, and a catalyst system comprising a reducing agent, or titanium, vanadium, zirconium, and tungsten. , A catalyst system comprising a metal halide such as molybdenum or an acetylacetone compound and an organoaluminum compound. The ring-opening polymerization reaction is carried out in a solvent or without a solvent, usually at a polymerization temperature of −50 ° C. to 100 ° C., 0 to 50 k.
It can be carried out at a polymerization pressure of g / cm ² .

The hydrogenated product of a ring-opening polymer of a norbornene-based monomer can be usually obtained by adding a hydrogenation catalyst to a polymerization solution of the above-described ring-opened polymer of a norbornene-based monomer and hydrogenating it. The hydrogenation catalyst is not particularly limited, but usually a heterogeneous catalyst or a homogeneous catalyst is used.

Examples of the heterogeneous catalyst include nickel, palladium, platinum, and solid catalysts in which these metals are supported on a carrier such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. Diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth,
Palladium / alumina and the like. As the homogeneous catalyst, for example, a catalyst comprising a combination of a transition metal compound and an alkylaluminum metal compound or alkyllithium, for example, cobalt acetate / triethylaluminum,
Cobalt acetate / triisobutylaluminum, nickel acetate / triethylaluminum, nickel acetate / triisobutylaluminum, nickel acetylacetonate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene chloride / n-butyllithium, zirconocene chloride / n-
A catalyst comprising a combination of butyllithium and the like can be mentioned. These hydrogenation catalysts can be used alone or in combination of two or more. The amount of the hydrogenation catalyst used is the amount of the ring-opened polymer 1 of the norbornene monomer.
The amount is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, per 100 parts by weight. The hydrogenation reaction is usually 1 to 150 kg
The reaction is carried out under a hydrogen pressure of / cm ² in a temperature range of 0 to 250 ° C and a reaction time of 1 hour to 20 hours.

On the other hand, an addition polymer of a norbornene-based monomer or another monomer copolymerizable with the norbornene-based monomer can be obtained according to a conventional method. As the norbornene-based monomer, for example, a norbornene-based monomer having no norbornane structure or a norbornene-based monomer having one or more norbornane structures is used. These norbornene monomers may be used alone or in combination of two or more.

The other monomer copolymerizable with the norbornene-based monomer is not particularly limited. Examples thereof include ethylene, propylene, 1-butene, 1-pentene and 1-pentene.
Hexene, 3-methyl-1-butene, 3-methyl-1-
Pentene, 3-ethyl-1-pentene, 4-methyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene , 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
C2-C20 ethylene or α-olefin such as 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-
Cyclohexene, cyclooctene, 3a, 5,6,7a
Cycloolefins such as -tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; Non-conjugated dienes;
And the like. These other monomers copolymerizable with the norbornene-based monomer can be used alone or in combination of two or more.

The ratio of the repeating unit derived from the norbornene monomer and the repeating unit derived from the other copolymerizable monomer in the addition polymer consisting of the norbornene monomer or the other monomer copolymerizable with the norbornene monomer is as follows: Although it may be appropriately selected according to the purpose of use, the molar ratio is usually 100: 0 to 10:90, preferably 90:10 to 15:85, more preferably 80:20 to 20:80. Range.

Addition polymers of norbornene-based monomers or other monomers copolymerizable with norbornene-based monomers are described in, for example, JP-A-60-168708, JP-A-61-120816, and JP-A-2-173112.
An addition polymerization catalyst disclosed in JP-A-5-9223 may be used. For example, a catalyst system comprising a monomer component in a solvent or without a solvent comprising a titanium, zirconium, or vanadium compound and an organic aluminum compound In the presence of is usually a polymerization temperature of -50 ℃ ~ 100 ℃, 0
It can be obtained by a method of addition (co) polymerization at a pressure of ５０50 kg / cm ² . The amount of the addition polymerization catalyst to be used is generally 1 to 10 ^-5 mmol / l, preferably 10 ^-1 to 10 ^-3 mmol / l as a transition metal atom. When the amount of the organic aluminum compound is expressed as a ratio of aluminum atoms to transition metal atoms (Al / M) in the polymerization reaction system, it is usually 1 to 10000, preferably 2 to 1000, and particularly preferably 3 to 100. In range.

The molecular weight of the norbornene-based polymer used in the present invention is appropriately selected according to the purpose of use. Gel permeation chromatography of a cyclohexane solution (a toluene solution when the polymer resin does not dissolve) is used. The weight average molecular weight in terms of polystyrene measured by the
000 or more, preferably 5,000 to 500,000,
When it is more preferably in the range of 8,000 to 200,000, particularly preferably in the range of 10,000 to 100,000, the molecular weight distribution (Mw / Mn) is 4.0 or less, preferably 3.5 or less, more preferably When the value is 3.0 or less, the mechanical strength and the moldability at the time of melt molding are highly balanced, which is preferable. The glass transition temperature (Tg) of the norbornene-based polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 70 ° C or higher, preferably 70 to 250 ° C, more preferably 80 to 200 ° C. ° C
When it is in the range, the heat resistance and the moldability during melt molding are highly balanced and suitable. ASTM of the norbornene-based polymer used in the present invention at 25 ° C.
The refractive index measured according to D542 may be appropriately selected according to the purpose of use, but is usually 1.46 to 1.60, preferably 1.50 to 1.56, more preferably 1.52 to 1.60.
When it is 56, it is suitable for light guide applications.

In the present invention, the phenolic antioxidant has the general formula (1)

[0030]

Embedded image

Where R¹Is H or lower alkyl
Group or an aryl group. Also, R ²Is H, or
A lower alkyl group, n represents an integer of 1 or 2; )

The use of a phenolic antioxidant having at least one structural unit represented by the formula:

By blending the phenolic antioxidant with the norbornene-based polymer, in a light guide having a long optical path length, the antioxidant itself has a small light absorption property and can be used even during melt molding and long-term use. It is very suitable because it hardly causes yellowing and has excellent coloring resistance. As R ¹ in the general formula (1), hydrogen, a lower alkyl group,
Although an aryl group is mentioned, it is preferable that R ¹ is hydrogen in order to highly balance the antioxidant effect and the color resistance. R ² in the general formula (1) includes hydrogen or a lower alkyl group. R ² is preferably hydrogen, and n is an integer of 1 or 2;
Is preferably 1. Thereby, the dispersibility with the norbornene-based polymer is increased, and at the same time, the coloring such as yellowing during melt molding or during use can be further reduced.

The phenolic antioxidant has at least one structural unit represented by the above general formula (1), usually 1 to 10, preferably 1 to 5, and more preferably 2 to 5. It has four. When the number of the structural units is within the above range, the coloring resistance and the solubility and dispersibility in the norbornene-based polymer when the molding material is melted and when the light guide is used for a long period of time are highly balanced, which is preferable. The structural unit is characterized in that it is bonded to an organic residue, but even if it is bonded to one specific atom of the organic residue, two or more specific May be bonded one by one to each of a plurality of the atoms, or may include those in which a plurality of the above structural units are bonded to the same atom in the organic residue. The organic residue is not particularly limited, but has 1 to 30 carbon atoms.
Are preferred, and those having an ester bond are more preferred.

As a specific example of the phenolic antioxidant represented by the general formula (1), one having one structural unit of the general formula (1) is 2-t-butyl-4-methyl-p
-Cresol, 2-tert-butyl-4-ethyl-6-methylphenol, stearyl-β- (3-tert-butyl-4
-Hydroxy-5-methylphenyl) propionate and the like,

The compound having two structural units of the general formula (1) includes 2,2'-methylenebis (4-methyl-6-
t-butylphenol), 2,2′-methylenebis (4
-Ethyl-6-t-butylphenol), 4,4′-thiobis (4-methyl-6-t-butylphenol),
4,4'-butylenebis (4-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2-
[Β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,
10-tetraoxaspiro [5,5] undecane and the like.

The compound having three or more structural units of the general formula (1) includes 1,1,3-tris (3-methyl-4-
(Hydroxy-5-t-butylphenyl) butane, 1,
3,5-trimethyl-2,4,6-tris (3-t-butyl-4-hydroxy-5-methylbenzyl) benzene, tetrakis- [methylene-3- (3′-t-butyl-4′-hydroxy) -5'-methylphenyl) propionate] methane, bis [3,3'-bis- (3'-t-
Butyl-4'-hydroxy-5'-methylphenyl) butyric acid] glycol ester, 1,3,5-
Tris (3'-t-butyl-4'-hydroxy-5'-
Methylbenzyl) -S-triazine-2,4,6- (1
(H, 3H, 5H) trione and the like. Among these phenolic antioxidants, a phenolic antioxidant containing two or more structures represented by the general formula (1) is preferable, and in particular, 3,9-bis [1,1-dimethyl-2-
[Β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,
10-tetraoxaspiro [5,5] undecane, tetrakis- [methylene-3- (3′-tert-butyl-4′-)
Hydroxy-5'-methylphenyl) propionate]
Methane is preferred.

The molecular weight of the phenolic antioxidant represented by the general formula (1) may be appropriately selected according to the desired molded product, but is usually 178 to 1500, preferably 300 to 1300, more preferably Is 500-110
When it is 0, it is preferable because it has excellent melt-kneading properties with a norbornene-based polymer and exhibits an antioxidant effect even in a small amount. These phenolic antioxidants represented by the general formula (1) can be used alone or in combination of two or more. The amount to be used is appropriately selected according to the purpose of use, but is usually 0.001 to 10 parts by weight, preferably 0.00 parts by weight, per 100 parts by weight of the norbornene-based polymer.
When the amount is in the range of from 0.5 to 5 parts by weight, and more preferably from 0.01 to 1 part by weight, the light transmittance and the coloring resistance of the light guide are highly balanced, which is preferable.

In the present invention, if necessary, other antioxidants can be used in combination with the phenolic antioxidant represented by the general formula (1). As other antioxidants, those commonly used in the industry can be used, and examples thereof include other phenolic antioxidants, phosphorus antioxidants, and sulfur antioxidants.
When used in combination with the phenolic antioxidant represented by the general formula (1), a long-term antioxidant effect may be exhibited.

Other phenolic antioxidants include, for example, 2-t-butyl-6- (3,5-di-t-
Butyl-2-hydroxybenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1-
(3,5-di-t-amyl-2-hydroxyphenyl)
JP-A-63-17 such as ethyl) phenyl acrylate
Acrylate compounds described in JP-A-9953 and JP-A-1-168463; octadecyl-3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-methylene-bis (4,6-
Di-t-butylphenol), 1,1,3-tris (2
-Methyl-4-hydroxy-5-t-butylphenyl)
Butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, tetrakis (methylene-3- (3 ′, 5′-
Alkyl substitution such as di-tert-butyl-4'-hydroxyphenylpropionate) methane [i.e., pentaerythrimethyl-tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionate)]). Phenolic compound; 6- (4-hydroxy-3,5-di-
t-butylanilino) -2,4-bisoctylthio-
1,3,5-triazine, 4-bisoctylthio-1,
3,5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino)-
Triazine group-containing phenolic compounds such as 1,3,5-triazine; and the like.

Examples of the phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2, 4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-
Monophosphite compounds such as 9-oxa-10-phosphaphenanthrene-10-oxide; 4,4′-
Butylidene-bis (3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'isopropylidene-bis (phenyl-di-alkyl (C12-C
15) Phosphites) and the like. Among these, a monophosphite compound is preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.

Examples of the sulfur-based antioxidants include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl.
3,3-thiodipropionate, laurylstearyl 3,3-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,2
4,8,10-tetraoxaspiro [5,5] undecane and the like.

These other antioxidants can be used alone or in combination of two or more with respect to the phenolic antioxidant of the present invention. It is appropriately selected within a range that does not impair.

Other Components In the present invention, other components can be added to the norbornene-based polymer, if necessary. Specific examples of other components include (a) other resins, (b) flexible polymers, and (c) other compounding agents other than antioxidants. These other components can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.

(A) Other resins Specific examples of the polymer other than the norbornene-based polymer used in the present invention include polystyrene, poly (meth) acrylate, polycarbonate, polyester, and the like.
Examples thereof include polyether, polyamide, polyimide, and polysulfone.

(B) Soft Polymer A soft polymer usually has a glass transition temperature (T
g), and also in the case of a polymer having a plurality of Tg or a polymer having both Tg and melting point (Tm), if the lowest Tg is 40 ° C. or lower, the soft weight is lower. Included in the union.

Examples of the soft polymer include isoprene rubber and its hydrogenated product; chloroprene rubber and its hydrogenated product; ethylene / propylene copolymer, ethylene / α-olefin copolymer, propylene / α-olefin copolymer Saturated polyolefin rubber such as ethylene / propylene / diene copolymer, α-olefin / diene copolymer, diene copolymer, isobutylene / isoprene copolymer, dibutyl copolymer such as isobutylene / diene copolymer, etc. Acrylonitrile / butadiene copolymer, hydrogenated product thereof; vinylidene fluoride / ethylene trifluoride copolymer, vinylidene fluoride / propylene hexafluoride Polymer, vinylidene fluoride, propylene hexafluoride, tetrafluoroethylene Rubber such as urethane rubber, silicone rubber, polyether rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, ethylene acrylic rubber, etc. Special rubber;

Random or block styrene-butadiene copolymers such as emulsion- or solution-polymerized styrene-butadiene rubber and high styrene rubber, and hydrogenated products thereof; styrene-butadiene-styrene rubber;
Styrene / isoprene / styrene rubber, random copolymer of aromatic vinyl rubber such as styrene / ethylene / butadiene / styrene rubber and conjugated diene, hydrogenated products thereof; styrene / butadiene / styrene rubber, styrene / isoprene / styrene rubber A linear or radial block copolymer of an aromatic vinyl monomer such as styrene / ethylene / butadiene / styrene rubber and a conjugated diene; a styrene-based thermoplastic elastomer such as a hydrogenated product thereof; a urethane-based thermoplastic elastomer; And thermoplastic elastomers such as polyamide-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, and fluorine-based thermoplastic elastomers.

(C) Other compounding agents As compounding agents other than antioxidants, those commonly used in the resin industry can be used, and specifically, ultraviolet absorbers, light stabilizers, near infrared absorbers , Coloring agents such as dyes and pigments, plasticizers, and organic or inorganic fillers.

As the ultraviolet absorber, for example, 2- (2
-Hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5)
-Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di -T-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2
-(3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-
benzotriazole-based ultraviolet absorbers such as t-amyl-2-hydroxyphenyl) -2H-benzotriazole;

4-tert-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4-di-tert-butylphenyl-3,5-di-t
-Butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2- (2H-benzotriazol-2-yl) -4
-Methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5
-T-octylphenyl) -2H-benzotriazole, 2- (2-hydroxy-4-octylphenyl)-
Bezoate UV absorbers such as 2H-benzotriazole;

2,4-dihydroxybenzophenone, 2
-Hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-dodecaroxy-2-fodroxybenzophenone, 4-benzyloxy Benzophenone ultraviolet absorbers such as -2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; ethyl-2-cyano-3, Acrylate ultraviolet absorbers such as 3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate;

[2,2'-thiobis (4-t-octylphenolate)]-2-complex ultraviolet absorbers such as nickel-ethylhexylamine nickel.

As the light stabilizer, for example, 2, 2, 6,
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl)
Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-
4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-
Hindered amine light stabilizers such as tetramethylpiperidine can be mentioned.

Examples of the near-infrared absorber include a cyanine-based near-infrared absorber; a pyrylium-based infrared absorber; a squarylium-based near-infrared absorber; a croconium-based infrared absorber;
Azurenium-based near-infrared absorber; phthalocyanine-based near-infrared absorber; dithiol metal complex-based near-infrared absorber;
Naphthoquinone-based near-infrared absorber; anthraquinone-based near-infrared absorber; indophenol-based near-infrared absorber; azimuth-based near-infrared absorber; In addition, commercially available near-infrared absorbers SIR-103, SIR-114, SIR
-128, SIR-130, SIR-132, SIR-
152, SIR-159, SIR-162 (manufactured by Mitsui Toatsu Dye), Kayasorb IR-750, Ka
yasorb IRG-002, Kayasorb I
RG-003, IR-820B, Kayasorb I
RG-022, Kayasorb IRG-023, Ka
yasorb CY-2, Kayasorb CY-
4, Kayasorb CY-9 (Nippon Kayaku)
And the like.

The dye is not particularly limited as long as it can be uniformly dispersed and dissolved in a thermoplastic polymer having an alicyclic structure. However, the dye has excellent compatibility with the alicyclic structure-containing polymer used in the present invention. Oil-soluble dyes (various CI solvent dyes) are widely used. Specific examples of oil-soluble dyes include The Society of Diyes and C
colorist vo, published by ourlists
l. Various C.3 described in C.3. I. And a solvent dye.

As the pigment, for example, diarylide pigments such as Pigment Red 38; Pigment Red 48:
2, Pigment Red 53, Pigment Red 57: 1
Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 248, etc. Condensed Azo Lake Pigments; Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 1
85, penzimidazolone pigments such as Pigment Red 208; quinacridone pigments such as Pigment Red 122; Pigment Red 149, Pigment Red 17
8, perylene pigments such as Pigment Red 179; and anthraquinone pigments such as Pigment Red 177.

As the plasticizer, for example, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenylcresyl phosphate, monophenyldicresyl phosphate, diphenylmonoxylenyl phosphate Phosphate triester plasticizers such as phosphate, monophenyldixylenyl phosphate, tributyl phosphate and triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-phthalate 2-ethylhexyl, diisononyl phthalate, octyldecyl phthalate,
Phthalate ester plasticizers such as butyl benzyl phthalate; fatty acid monobasic ester plasticizers such as butyl oleate and glycerin monooleate; dihydric alcohol ester plasticizers; oxyester ester plasticizers;
Among them, a phosphoric acid triester plasticizer is preferable, and tricresyl phosphate and tricillyl phosphate are particularly preferable.

Further, specific examples of the plasticizer include squalane (C30H62, Mw = 422.8), liquid paraffin (white oil, ISO VG10, ISO VG15, ISO VG15 specified in JIS K2231).
32, ISO VG68, ISO VG100, VG8
And VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene, and the like. Among them, squalane, liquid paraffin and polyisobutene are preferred. The organic or inorganic filler is not particularly limited as long as it is generally used in the polymer industry.

As the organic filler, ordinary organic polymer particles or crosslinked organic polymer particles can be used.
Specifically, for example, polyethylene, polypropylene,
Polyolefins such as polymethyl-1-butene, poly-4-methyl-1-pentene and poly1-butene; halogen-containing vinyls such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, polychloroprene, and chlorinated rubber Polymers: α, β- such as polyarylate, polymethacrylate, polyacrylamide, polyacrylonitrile, acrylonitrile-butadiene-styrene copolymer, polyacrylonitrile, acrylonitrile-styrene-acrylate (co) polymer, etc.
(Co) polymers derived from unsaturated acids or derivatives thereof;

Polyvinyl alcohol, polyvinyl acetate,
Derived from unsaturated alcohols such as poly (vinyl stearate), poly (vinyl benzoate), poly (vinyl maleate), poly (vinyl bitilal), poly (allyl phthalate), poly (allyl melatin), ethylene / vinyl acetate copolymer and amines or their acyl derivatives or acetal Polymer;
Polymers derived from polyethylene oxide or bisglycidyl ether; polyphenylene oxide; polycarbonate; polysulfone; polyurethane; and urea resins;
Polyamides such as nylon 11 and nylon 12; Polyesters such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol / cyclohexane terephthalate; Or a polymer having a crosslinked structure derived from melamine, for example, natural polymer compounds such as cellulose acetate, cellulose propionate, and cellulose ether; and particles or crosslinked particles.

Inorganic fillers include groups 1, 2, 4 and 6.
Oxides, hydroxides, sulfides, nitrides of the elements of Group 7, Group 7, 8 to 10, Group 11, Group 12, 13 or 14;
Halides, carbonates, sulfates, acetates, phosphates, phosphites, organic carboxylates, silicates, titanates, borates, and hydrated compounds thereof, and composite compounds containing these compounds, Natural mineral particles with a chemical composition. Specifically, Group 1 element compounds such as lithium fluoride and borax (hydrated sodium borate); magnesium carbonate, magnesium phosphate, magnesium oxide, magnesium chloride, magnesium acetate, magnesium fluoride, magnesium titanate, magnesium silicate, and silicate Magnesium hydrate (talc), calcium carbonate, calcium phosphate, calcium phosphite, calcium sulfate (gypsum), calcium acetate, calcium terephthalate, calcium hydroxide, calcium silicate, calcium fluoride, calcium titanate, strontium titanate, carbonate Group 2 element compounds such as barium, barium phosphate, barium sulfate and barium phosphite;

Titanium dioxide (titania), titanium monoxide, titanium nitride, zirconium dioxide (zirconia),
Group 4 element compounds such as zirconium monoxide; 6 such as molybdenum dioxide, molybdenum trioxide and molybdenum sulfide
Group 7 element compounds; 7 such as manganese chloride and manganese acetate
Group 8 compounds; 8 such as cobalt chloride and cobalt acetate
Group 10 element compounds; Group 11 element compounds such as cuprous iodide; Group 12 element compounds such as zinc oxide and zinc acetate;
Group 13 element compounds such as aluminum oxide (alumina), aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite); silicon oxide (silica, silica gel), graphite, carbon, graphite,
Group 14 element compounds such as glass; and particles of natural minerals such as kernalite, kainite, mica (mica, kinunmo), and virose ore.

In the present invention, it is particularly preferable to add an anti-opacity agent as a compounding agent, without impairing various properties of the norbornene-based polymer such as transparency, low moisture absorption, heat resistance and mechanical strength. Prevents white turbidity in a high temperature and high humidity environment. Examples of the anti-opacity agent include the above-mentioned soft polymer, the above-mentioned organic or inorganic filler, an alcoholic compound, and at least one compound selected from the group consisting of a compound incompatible with a norbornene-based polymer. Of these, alcoholic compounds and soft polymers are preferable, and soft polymers are particularly preferable, in order to highly balance transparency, heat resistance, moldability and white turbidity prevention under high temperature and high humidity environments.

Among the above soft polymers, from the viewpoint of preventing cloudiness, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer and a hydrogenated product thereof have good dispersibility in a norbornene polymer composition. Is preferred. The copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. From the viewpoint of heat resistance, a hydrogenated copolymer in which a portion other than the aromatic ring is hydrogenated is more preferable. Specific examples of such a soft polymer include, for example, a hydrogenated product of a homopolymer such as polybutadiene, a hydrogenated product of a random copolymer such as a butadiene / styrene copolymer; butadiene / styrene /
Block copolymer, styrene, butadiene, styrene,
Block copolymers, hydrogenated block copolymers such as isoprene / styrene / block copolymers and styrene / isoprene / styrene / block copolymers; and the like.

Among the organic or inorganic fillers,
The average particle size is appropriately selected depending on the intended use,
The average particle diameter of [(major axis + minor axis) / 2] is usually 0.01 to
When it is in the range of 50 μm, preferably 0.1 to 30 μm, the transparency and the effect of preventing white turbidity in a high-temperature and high-humidity environment are highly balanced and suitable. The shape of the particles is not particularly limited, but spherical particles having a ratio of the length of the long side to the length of the short side of 2: 1 or less are preferable. Examples of the alcoholic compound include a compound having at least one alcoholic hydroxyl group and at least one ether bond, and a compound having at least one alcoholic hydroxyl group and at least one ester bond. A compound having at least one alcoholic hydroxyl group and at least one ether bond is an organic compound having at least one alcoholic hydroxyl group that is not a phenolic hydroxyl group and at least one ether bond unit in the molecule. It is not particularly limited as long as it is a compound. For example, preferably a polyhydric alcohol having 2 or more valencies, more preferably 3 to 8
A partial ether compound in which a part of hydroxyl groups such as a polyhydric alcohol having one hydroxyl group is etherified is exemplified.

The compound having at least one alcoholic hydroxyl group and at least one ester bond includes at least one alcoholic hydroxyl group other than a phenolic hydroxyl group and at least one ether bond unit in the molecule. There is no particular limitation as long as it is an organic compound having two or more compounds. For example, a partial ester compound in which a part of hydroxyl groups is esterified, such as a polyhydric alcohol having preferably 2 or more hydroxyl groups, and more preferably a polyhydric alcohol having 3 to 8 hydroxyl groups, may be mentioned. Examples of the dihydric or higher polyhydric alcohol include polyethylene glycol, glycerol, trimethylolpropane, pentaerythritol, diglycerol, triglycerol, dipentaeristol, 1,6,7-trihydroxy-2,2-diol. (Hydroxymethyl) -4-oxoheptane, sorbitol, 2-methyl-1,6,7-trihydroxy-2-
Hydroxymethyl-4-oxoheptane, 1,5,6-
Trihydroxy-3-oxohexanepentaerythol, tris (2-hydroxyethyl) isocyanurate and the like, among which trihydric or higher polyhydric alcohols and polyhydric alcohols having 3 to 8 hydroxyl groups Is preferred. In order to obtain a partially esterified compound,
Glycerol, diglycerol, triglycerol, and the like, which can synthesize a partially esterified product containing α, β-diol, are preferred.

Specific examples of such partially etherified or partially esterified products include glycerin monostearate, glycerin monolaurate, glycerin monobehenate, diglycerin monostearate, glycerin distearate, glycerin dilaurate, and the like. Esterified products of polyhydric alcohols such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol beherate, pentaerythritol dilaurate, pentaerythritol tristearate, dipentaerythritol distearate, and the corresponding etherified products; 3- (octyloxy)-
1,2-propanediol, 3- (lauryloxy)-
1,2-propanediol, 3- (4-nonylphenyloxy) -1,2-propanediol, 1,6-dihydroxy-2,2-di (hydroxymethyl) -7- (4-
Nonylphenyloxy) -4-oxoheptane, an etherified product obtained by reacting a condensate of p-nonylphenyl ether with an aldehyde and glycidol, an ether obtained by reacting a condensate of p-octylphenyl ether with dicyclopentadiene and glycidol And the like.

The molecular weight of these alcoholic compounds is
Although it is not particularly limited, it is usually 100 to 3000, preferably 200 to 2000, and more preferably 300 to 1500.
When the ratio is within the range, the transparency and the clouding prevention effect are highly balanced and suitable.

The compound incompatible with the norbornene-based polymer is a compound other than the alcoholic compound, the organic or inorganic filler, and the soft polymer, and is incompatible with the norbornene-based polymer. . The compound incompatible with the norbornene-based polymer is not particularly limited as long as it is an incompatible compound that is not completely dissolved in the norbornene-based polymer. The incompatibility is determined according to the ordinary method in the resin industry. For example, a molded product obtained by melt-mixing 5 parts by weight of a compound with respect to 100 parts by weight of a norbornene-based polymer is observed with an electron microscope at a magnification of 100,000, and a domain or particle of 1 mm ² or more within a range of 10 cm × 15 cm is obtained. Having at least one is defined as incompatible. As the incompatible compound, a resin other than the norbornene-based polymer is usually used. Other resins incompatible with the norbornene-based polymer include, for example, polyphenylene sulfide, polyether such as polyphenylene ether or polythioether; aromatic polyester, polyarylate, polyethylene terephthalate,
Polyester polymers such as polybutylene terephthalate, polycarbonate and polyether ketone; polyethylene, polypropylene, poly 4-methyl-pentene-1
General-purpose transparent resins such as polymethyl methacrylate, cyclohexyl methacrylate and methyl methacrylate copolymer, polyacrylonitrile styrene (AS resin); acrylic resins; M
S resin; liquid crystal plastic and the like.

When a compound incompatible with these norbornene-based polymers is added, a large number of dispersed microdomains are formed in the molded article in many cases. In the case of forming micro domains, the average particle diameter [(major axis + minor axis) / 2] of the domains observed with an electron microscope is usually 0.001 to 0.
When the size is 5 μm, preferably 0.005 to 0.3 μm, and particularly preferably 0.01 to 0.2 μm, the transparency of the molded article and the effect of preventing white turbidity in a high-temperature and high-humidity environment are highly balanced. It is preferred. The refractive index of these anti-opacity agents may be appropriately selected according to the purpose of use, but the difference from the refractive index of the norbornene-based polymer is usually 0.5 or less, preferably 0.2 or less, more preferably Those having a value of 0.1 or less are preferred because transparency and anti-cloudiness in a high-temperature and high-humidity environment are highly balanced.

These anti-opacity agents are each used alone,
Alternatively, two or more kinds can be used in combination. The mixing ratio of the anti-opacity agent may be appropriately selected within a range in which the anti-opacity effect can be exhibited.
Usually, 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 5 parts by weight with respect to 0 parts by weight
When blended at a ratio of 2 parts by weight, the heat resistance, the transparency, and the effect of preventing white turbidity in a high-temperature and high-humidity environment are highly balanced and suitable.

Molding Material The molding material used in the present invention comprises, as essential components, the norbornene-based polymer and the phenolic antioxidant represented by the general formula (1), and optionally the other components. Can be blended. As a molding material, a twin-screw kneader is usually used, and after kneading, it is often extruded into a rod in a molten state, cut into a suitable length by a strand cutter, and pelletized.

Molding Method The molded article of the present invention can be obtained by melt-molding the above molding material. The melt molding method is not particularly limited, and examples thereof include hot press molding, extrusion molding, and injection molding. Injection molding is preferable from the viewpoint of moldability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the resin temperature in the injection molding method is usually 150 to 400 ° C., preferably 180 to 36 ° C.
The temperature is appropriately selected within the range of 0 ° C, more preferably 190 to 330 ° C, particularly preferably 200 to 300 ° C. If the resin temperature is excessively low, the fluidity will deteriorate, and the molded product will have sink marks and distortion.If the resin temperature is excessively high, silver streaks will occur due to thermal decomposition of the resin, and the molded product will turn yellow, etc. Failure may occur.

In the case of performing injection molding, usually, the molding material is injected into a mold after being melted in a cylinder. The above-described setting of the resin temperature is performed based on the cylinder temperature at this time. The molding material is usually put into a hopper,
It is sent to the cylinder by a screw whose number of revolutions is set so that the molding materials are uniformly mixed. The injection speed from the cylinder to the mold is usually 10 to 1000 cm ³ / sec.
When it is c, it is possible to mold a molded article having a long optical path with high accuracy, which is preferable. The injection pressure from the cylinder to the mold may be appropriately selected and set in consideration of the design of the mold, the flowability of the norbornene-based polymer to be used, and the like, and is usually set to 500 to 1500 kgf / cm ² . Done in a range.

The holding pressure is a pressure applied for a certain period of time after the molding material is substantially filled into the mold from the cylinder by the injection pressure until the gate portion of the mold is completely cooled and solidified. Is generally set within a range of clamping pressure of the mold as the upper limit of pressure holding, usually 2,000 kgf / cm ² or less,
Preferably, it is set in the range of 1700 kgf / cm ² or less, more preferably 1500 kgf / cm ² or less. By setting the upper limit of the holding pressure in such a range, there is no possibility that molding failure such as distortion occurs in the molded product.
The lower limit of the holding pressure is at least 100 kgf / cm
² or more, preferably 120 kgf / cm ² or more, more preferably set in the 150 kgf / cm ² or more ranges. By keeping the lower limit of the holding pressure in such a range,
The occurrence of sink marks in the molded product can be prevented, the molding shrinkage can be reduced, and a molded product with excellent dimensional accuracy can be obtained.

The mold temperature is usually set at a temperature lower than the glass transition temperature (Tg) of the norbornene-based polymer.
Preferably, the Tg of the norbornene-based polymer is 0 to 10 or more.
0 ° C. lower range, more preferably 20 to less than Tg.
It is set in a range lower by 60 ° C. By setting the mold temperature in such a range, the distortion of the molded product can be suppressed to a low level.

Preliminary drying of the molding material may be performed in advance for the purpose of minimizing the deterioration of the color tone of the molded product and the generation of carbides and voids. As the drying conditions, the temperature is usually 50 to 200 ° C, preferably 80 to 150 ° C, more preferably 100 to 110 ° C, and the time is generally 1 to 100 hours, preferably 2 to 50 hours, more preferably 4 to 12 hours.
It is preferable to perform vacuum drying for a long time or to flow nitrogen or the like from the hopper of the injection molding machine to replace the air with air.

The light guide of the present invention thus obtained is a kind of an optical member, and means a member that guides light generated from a light source from at least one end face to the other end. The shape of the light guide is not particularly limited, and may be a rod, a plate, a fiber,
In addition, various shapes such as those having a complicated shape are included. Specific examples include optical fibers, light guides for vehicle lamps, light guide plates, light guides for various instruments, and the like, and are particularly suitable for light guide plates having a large screen size, and among them, the edge light type light guide plates are more preferable. .

In the present invention, the light transmission effect is particularly remarkable in a light guide having a long optical path length, which is preferable. The optical path length is a distance from one end face of the light guide into which light from the light source is incident, to one end face from which light is incident on the light guide and which is emitted farthest linearly, and usually 100 mm or more, preferably Is preferable because the effect of the present invention is remarkably exhibited in a light guide of 130 mm or more, more preferably 150 mm or more.

[0081]

EXAMPLES Hereinafter, the present invention will be described based on examples that further embody the present invention, in comparison with comparative examples. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “parts” and “%” are based on weight unless otherwise specified. In the following Production Examples, Examples and Comparative Examples, methods for measuring various physical properties are as follows.

(1) The refractive index is ASTM at 25 ° C.
A value measured according to D542. (2) The hydrogenation rate was calculated by ¹ H-NMR measurement. (3) The glass transition temperature (Tg) is JIS-K7121.
Is the value measured based on (4) Transparency was measured using a spectrophotometer (product number U-30 manufactured by JASCO Corporation) by continuously changing the wavelength in the wavelength range of 400 to 900 nm and measuring the light transmittance (%). Was measured as the light transmittance of the light guide plate. The higher the light transmittance, the better the transparency. (5) The light transmittance was measured by using a luminance meter (BM-7: manufactured by Topcon Co., Ltd.), and the light-emitting surface of the light guide plate (a rectangular surface 1.5 cm inside from the periphery of the molding surface of the light guide plate) on the long and short sides. The luminance (vertical direction) of a total of 9 points was measured at equal intervals, and the average value was calculated.

(6) As in the case of (5), color temperature spots were measured to evaluate light transmittance. Using a luminance meter (BM-7: manufactured by Topcon Corporation), the light-emitting surface of the light guide plate (a rectangular surface 1.5 cm inside from the periphery of the molding surface of the light guide plate) is equidistant from the light source to the nearest and farthest portions from the light source. The color temperature difference (vertical direction) at each of the five points was measured, and the color temperature difference was evaluated by the average of the color temperature of the farthest part−the average of the color temperature of the closest part, and evaluated according to the following criteria. The smaller the color temperature spot, the better the light transmittance in the long light path. ◎: 500K or less ○: Over 500K and 1,000K or less △: Over 1,000K and 1,500K or less ×: Over 1,500K (7) The light resistance was measured with a fade meter (black panel temperature 63 ° C, (120 hours) The luminance of the light guide plate after irradiation with ultraviolet rays was measured in the same manner as in (4).

(Production Example 1) Under nitrogen atmosphere, 250 parts by weight of dehydrated cyclohexane, 1.20 parts by weight of 1-hexene diluted with 10 parts by weight of cyclohexane, 0.11 part by weight of dibutyl ether, and 0.1 part by weight of triisobutylaluminum.
After mixing 22 parts by weight in a reactor at room temperature, 8-ethyltetracyclo [4.4.1] was maintained at 45 ° C.
^2,5 . ^{17 , 10} . 100 parts by weight of [0] -dodec-3-ene (hereinafter abbreviated as ETCD) and 30 parts by weight of a toluene solution of 0.70% by weight of tungsten hexachloride were continuously added over 2 hours to carry out polymerization. The prepared polymerization reaction solution was directly transferred to a pressure-resistant hydrogenation reactor, and 10 parts by weight of a diatomaceous earth-supported nickel catalyst was added.
The reaction was performed at kgf / cm ² for 10 hours. This solution is
The catalyst was removed by filtration with a filter equipped with a stainless steel wire mesh using diatomaceous earth as a filter aid. To this hydrogenated polymer solution, 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl as an antioxidant was added. ]
2,4,8,10-Tetraoxaspiro [5,5] undecane was added in an amount of 1.0 to 100 parts by weight of the hydrogenated polymer.
After adding parts by weight, the solvent was removed at 280 ° C. while drying under reduced pressure. Next, the molten resin was pelletized by an extruder under a nitrogen atmosphere. To 100 parts by weight of the pellets, 0.4 part by weight of a hydrogenated styrene / butadiene / styrene / block copolymer (ToughTech H1051 manufactured by Asahi Kasei Kogyo Co., Ltd.) was mixed, kneaded with a twin-screw kneader, and passed through a strand cutter. A pellet (granular) molding material (A) was obtained.

The molding material had a refractive index of 1.53, a hydrogenation rate of 99.9%, a glass transition temperature (Tg) of 140 ° C.
Light transmittance 92%, weight average molecular weight (Mw) of the norbornene-based polymer obtained by high performance liquid chromatography (in terms of polyisoprene) using cyclohexane as a moving layer.
Is 29,000, and molecular weight distribution (Mw / Mn) is 2.4.
It was 8.

(Production Example 2) Instead of 100 parts by weight of ETCD, 15 parts by weight of ETCD and tricyclo [4.3.1] were used.
^2,5 . 0 ^1,6 ] deca-3,7-diene (dicyclopentadiene, hereinafter referred to as DCP) in an amount of 85 parts by weight (100 parts by weight in total), and 1-hexene was added in an amount of 0.93 parts.
Except for using parts by weight, a molding material (B) was obtained in the same manner as in Production Example 1. The molding material has a refractive index of 1.53, a hydrogenation rate of 99.9%, and a glass transition temperature (Tg) of 103.
° C and light transmittance 92%. The weight average molecular weight (Mw) of the norbornene-based polymer in the molding material was 31,000.

(Production Example 3) 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-), an antioxidant
4-Hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane was added in an amount of 1.2 parts by weight based on 100 parts by weight of the hydrogenated polymer. Except for the above, a molding material (C) was obtained in the same manner as in Production Example 2. The refractive index of this molding material was 1.53, the hydrogenation rate was 99.9%, and the glass transition temperature (T
g) was 103 ° C. and the light transmittance was 92%.

(Production Example 4) 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-), an antioxidant
4-Hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane was added in an amount of 0.2 part by weight based on 100 parts by weight of the hydrogenated polymer. Except for the above, a molding material (D) was obtained in the same manner as in Production Example 2. The refractive index of this molding material was 1.53, the hydrogenation rate was 99.9%, and the glass transition temperature (T
g) was 103 ° C. and the light transmittance was 92%.

(Production Example 5) 3,9-bis [1,1-dimethyl-2- [β- (3-t-butyl-), an antioxidant
4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane was added in an amount of 0.05 part by weight based on 100 parts by weight of the hydrogenated polymer. A molding material (E) was obtained in the same manner as in Production Example 2 except for the above. The refractive index of this molding material was 1.53, the hydrogenation rate was 99.9%, and the glass transition temperature (T
g) was 103 ° C. and the light transmittance was 92%.

Examples 1 to 5 The pellets of the molding materials (A) to (E) obtained in Production Examples 1 to 5 were injection-molded to produce light guide plates (A) to (E). The molding conditions for the injection molding were as follows: using an injection molding machine of product number IS450 manufactured by Toshiba Machine Co., Ltd.
0 ° C, cylinder temperature 290 ° C, nozzle temperature 260 ° C,
Injection pressure 1000 kgf / cm ² , holding pressure 800 kgf /
cm ² , mold clamping pressure 1200 kgf / cm ² , injection speed (corresponding to screw advance speed) 40 cm ³ /
s, screw back pressure 70 kgf / cm ² , and screw rotation speed 30 rpm. The time from the start of filling into the mold to the end of filling was 1 second.

The obtained light guide plates (A) to (E) have a thickness at one end of 2.0 mm, a thickness at the end side of 0.5 mm, a length from one end to the end side of 190 mm, and a linear light source. The length along the axial direction was 250 mm, and the wedge shape was such that the thickness gradually decreased in the direction away from one end to the end (in a direction substantially perpendicular to the axis of the linear light source). A reflective tape of product number RF188 manufactured by Tsujimoto Electric Co., Ltd. was attached to the side end surface of the light guide plate thus obtained other than the light incident end surface, and a tube manufactured by Harrison Electric Co., Ltd. was attached to the short side light incident end portion. Install a 2.4mm diameter cold cathode lamp,
An edge light type planar light source unit was produced by covering the periphery of the lamp and the light incident portion of the light guide plate with a reflector of product number GR38W manufactured by Kimoto Corporation. Using this unit, luminance, color temperature unevenness, and light resistance were evaluated.
The above results are summarized in Table 1.

[0092]

[Table 1]

Comparative Example 1 A molding material (G) was obtained in the same manner as in Production Example 2 without adding an antioxidant. The molding material has a refractive index of 1.53, a hydrogenation rate of 99.9%, and a glass transition temperature (Tg) of 103.
° C and light transmittance 92%. Using this molding material (G), molding was performed in the same manner as in Example 1, and a light guide plate (F) was obtained to produce an edge light type on-surface light source unit. Using this unit, luminance, color temperature unevenness, and light resistance were evaluated. The above results are summarized in Table 1.

Comparative Example 2 As an antioxidant, pentaerythrityl-tetrakis (3
Molding material in the same manner as in Production Example 2 except that 0.5 parts by weight of-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate) was added to 100 parts by weight of the hydrogenated polymer. (H) was obtained. This molding material had a refractive index of 1.53, a hydrogenation rate of 99.9%, a glass transition temperature (Tg) of 103 ° C., and a light transmittance of 92%. Using this molding material (H), molding was performed in the same manner as in Example 1,
The light guide plate (I) was obtained, and an edge light type surface light source unit was prepared. Using this unit, luminance, color temperature unevenness, and light resistance were evaluated. Table 1 summarizes the above results.
Shown in

From the above Examples and Comparative Examples, the light guide of the present invention exhibits excellent characteristics in average luminance, unevenness in color temperature, and luminance after the light resistance test. In the compounded light guide (Examples 1, 2, and 3), the average luminance was high, the color temperature unevenness was very good, and the polymer used for the resin material had a specific structure. It can be confirmed that (Example 2) is excellent in the above characteristics.

[0096]

According to the present invention, transparency and light resistance are excellent,
Light absorption of the antioxidant itself is low, and during molding, yellowing hardly occurs even during long-term use,
A resin material which can reduce the amount of the antioxidant and is very suitable for a light guide having a long optical path length, and a light guide obtained by the resin material are provided.

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Claims (4)

[Claims] 1. A norbornene polymer and a compound represented by the general formula (1): ## STR1 ## (Wherein, R ¹ represents hydrogen or a lower alkyl group or an aryl group; R ² represents hydrogen or a lower alkyl group; and n represents an integer of 1 or 2). A light guide formed by molding a molding material comprising a phenolic antioxidant having at least one structural unit. 2. The light guide according to claim 1, wherein the norbornene-based polymer contains at least a repeating unit having no norbornane structure. 3. The light guide according to claim 1, wherein an optical path length of the light guide is 100 mm or more. 4. The light guide according to claim 1, wherein the light guide is a light guide plate.