JP2008208237A - Molded product of cycloolefin addition polymer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molded product obtained by carrying out melt molding of a composition containing a cycloolefin addition polymer and a lubricant and having excellent transparency and heat resistance. <P>SOLUTION: The molded product is obtained by carrying out melt molding of a resin composition having 5% weight reduction temperature of ≥300°C under nitrogen atmosphere, containing a lubricant and a cycloolefin addition polymer and having 230-400°C glass transition temperature. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a molded article having excellent transparency and heat resistance, obtained by melt-molding a cyclic olefin addition polymer composition.

  Conventionally, inorganic glass is generally used as an optical material for lenses, liquid crystal display elements, color filters, EL display element substrates, backlights, light guide plates, and the like. However, inorganic glass has drawbacks such as being easily broken, lacking in flexibility, large specific gravity, and poor workability. In recent years, there has been a demand for lighter, smaller, and higher density optical materials. Therefore, transparent resins that meet these requirements are used in place of inorganic glass. The acrylic resin and polycarbonate resin used as the transparent resin have low heat resistance.

  The cyclic olefin addition polymer is a transparent resin having high heat resistance. The cyclic olefin addition polymer or the composition thereof is molded by a casting method or a melt molding method. The solubility of the cyclic olefin addition polymer in a general solvent is low, and it is difficult to mold the cyclic olefin addition polymer or a composition thereof by a casting method. Therefore, a method for producing a cyclic olefin addition polymer film or sheet in which a solution obtained by dissolving a cyclic olefin addition polymer containing a specific structural unit in a specific organic solvent is formed by a cast method was studied. (For example, refer to Patent Document 1). However, the cyclic olefin addition polymer film or sheet produced by the casting method contains an organic solvent.

On the other hand, a method for producing a light diffusive molded article having excellent light transmittance, in which a light diffusing resin composition containing an addition polymer of a norbornene monomer and fluororesin particles is melt-molded (for example, a patent) Reference 2). The melt molding of the composition of the cyclic olefin addition polymer, which is a polymer having high heat resistance, is performed at a high temperature, and a lubricant may be added to the composition in order to improve the moldability of the composition. Conventionally, the influence of a lubricant on the transparency of a molded product obtained by melt-molding a cyclic olefin addition polymer composition has not been studied.
JP 2004-74662 A JP 2004-149610 A

  The problem to be solved by the present invention is to provide a molded article having excellent transparency and heat resistance obtained by melt-molding a composition containing a cyclic olefin addition polymer and a lubricant.

The present invention includes a lubricant having a 5% weight loss temperature of 300 ° C. or higher under a nitrogen atmosphere and a cyclic olefin addition polymer, and a resin composition having a glass transition temperature of 230 to 400 ° C. is melt-molded. A molded body.
In a preferred embodiment of the present invention, the lubricant is contained in an amount of 0.5 to 15 parts by mass with respect to 100 parts by mass of the cyclic olefin addition polymer.
In another preferred embodiment of the invention, the lubricant comprises a hydrocarbon.
In another preferred embodiment of the present invention, the molded body is an optical component.

  The molded article of the present invention has excellent transparency and heat resistance, and is useful as an optical material.

(Cyclic olefin addition polymer)
Specific examples of the cyclic olefin addition polymer used in the present invention include addition polymers of alicyclic monomers having a norbornene ring, alicyclic monomers having a norbornene ring, and other monomers. It is an addition copolymer. Specific examples of the alicyclic monomer having a norbornene ring are: (a) Unsaturation other than the carbon-carbon unsaturated bond involved in the addition polymerization reaction such as norbornene, tetracyclododecene, and alkyl-substituted products thereof. A monomer having no bond; (b) a monomer having an unsaturated bond other than the carbon-carbon unsaturated bond involved in the addition polymerization reaction, such as ethylidene norbornene, vinyl norbornene, ethylidetetracyclododecene, dicyclopentadiene, etc. A monomer having an aromatic ring such as (c) dimethanotetrahydrofluorene and phenylnorbornene, and (d) a monomer having a polar group such as methoxycarbonylnorbornene and methoxycarbonyltetracyclododecene. These alicyclic monomers having a norbornene ring are used independently or in combination of two or more.

  Specific examples of the monomer copolymerizable with the alicyclic monomer having a norbornene ring include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene. Styrenes such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; carbon monoxide It is.

  The cyclic olefin addition polymer used in the present invention may have a polar group. Specific examples of the method for introducing a polar group include (1) a method in which a polar group-containing unsaturated compound is added by graft modification, and (2) when a carbon-carbon unsaturated bond is present in a cyclic olefin addition polymer, A method in which a polar group is added to the unsaturated bond, and (3) a method in which a monomer having a polar group is copolymerized. Specific examples of the polar group are an epoxy group, a carboxyl group, a hydroxyl group, an ester group, a silanol group, an amino group, a nitrile group, a halogen group, an acyl group, and a sulfone group. Preferred polar groups are an epoxy group, a hydroxyl group, a silanol group, an amino group, and a carboxyl group.

  In the cyclic olefin addition polymer used in the present invention, the total of the following repeating units (a) and repeating units (b) is usually 70 mol% or more, preferably 90 mol% or more of all repeating units, Is a norbornene compound addition polymer having a molar ratio [(a) / (b)] of the repeating unit (a) to the repeating unit (b) in the range of 10/90 to 98/2.

[Repeating unit (a)]
The repeating unit (a) is composed only of carbon and hydrogen, and is a repeating unit of a norbornene compound monomer in which all carbons are involved in the structure of the condensed ring skeleton. A specific example of such a repeating unit (a) is a repeating unit represented by the general formula (1).

Here, in the general formula ^{(1), R 1, R} 2 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When R ¹ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, they are bonded to each other to form a ring structure having no substituent. m is an integer of 0-2. Specific examples of the ring structure include a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a benzene ring, a cyclooctane ring, a cyclooctene ring, a norbornane ring, and a polycyclic structure in which a plurality of these rings are condensed.

  The repeating unit (a) is obtained by addition polymerization of the norbornene compound (A) represented by the general formula (2).

Wherein, R ^1, R ² and m are the same as R ^1, R ² and m in the general formula (1).

Specific examples of the norbornene compound (A) include 2-norbornene, dicyclopentadiene, tricyclo [5.2.1.0 ² , 6] dec-8-ene, tricyclo [6.2.1.02, ⁷ ] undeca. 9-ene, tricyclo [6.2.1.02, ^7] undec-4,9-diene, tricyclo [8.2.1.02, ^9] trideca-11-ene, tricyclo [8.2.1 .02, ^9] trideca -5, LL-diene, tetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, tetracyclo [9.2.1.02, ^10. 03, ^8] tetradeca -3,5,7,12- tetraene ( "1,4-methano -1,4,4a, 9a- tetrahydro -9H- fluorene" also called.), Tetracyclo [10.2.1. 02, ¹¹ . 04, ^9] pentadeca -4,6,8,13- tetraene ( "1,4-methano -1,4,4a, 9,9a, 10- hexahydro-anthracene," also called.), Pentacyclo [9.2. 1.1 ³ · ⁹ . 02, ¹⁰ ] pentadeca-12-ene, pentacyclo [9.2.1.13, ⁹ . 02, ^10] pentadeca-5,12-diene, pentacyclo [9.2.1.14, ^7. 02, ¹⁰ ] pentadeca-12-ene.
Preferred norbornene compounds (A) are 2-norbornene, tricyclo [5.2.1.02, ⁶ ] dec-8-ene, tricyclo [6.2.1.02] having no unsaturated bond other than the norbornene ring. ⁷ ] undec-9-ene, tricyclo [8.2.1.0 ^2,9 ] tridec-11-ene, tetracyclo [6.2.1.13, ⁶ . 02, ⁷ ] dodec-4-ene, pentacyclo [9.2.1.13, ⁹ . 0 ^2,10] pentadeca 12-ene, pentacyclo [9.2.1.14, ^7. 02, ¹⁰ ] pentadeca-12-ene. More preferred norbornene compounds (A) are 2-norbornene and tetracyclo [6.2.1.13, ⁶ . 02, ^7] dodecamethylene-4-ene. A particularly preferred norbornene compound (A) is 2-norbornene.

[Repeating unit (b)]
The repeating unit (b) is composed only of carbon and hydrogen, and a part of hydrogen of the norbornene compound monomer in which all the carbons are involved in the configuration of the condensed ring skeleton is substituted with 1 to 5 carbon atoms. It is a repeating unit of a norbornene compound monomer having a structure substituted only with a hydrocarbon group. A specific example of the repeating unit (b) is a repeating unit represented by the general formula (3).

In the general formula (3), R ^{3 to} R ⁶ are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and all of R ^{3 to} R ⁶ are not hydrogen atoms. When two or more of R ^{3 to} R ⁶ are hydrocarbon groups having 1 to 5 carbon atoms, they may be bonded to each other to form a ring structure having no substituent. n is an integer of 0-2.

  The repeating unit represented by the general formula (3) is obtained by addition polymerization of the norbornene compound (B) represented by the general formula (4).

Here, R ³ to R ⁶ and n are the same as R ³ to R ⁶ and n in the general formula (3).

Specific examples of the norbornene compound (B) include norbornenes having an alkyl group having 2 or less carbon atoms, such as 5-methyl-2-norbornene, 5-ethyl-2-norbornene, and 5,6-dimethyl-2-norbornene; Norbornenes having an alkenyl group having 2 or less carbon atoms such as 5-vinyl-2 norbornene; norbornenes having an alkylidene group having 2 or less carbon atoms such as 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, etc. 9-methyltetracyclo [6.2.1.13, ⁶ . 02, ^7] dodeca-4-ene, 9-ethyl-tetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, 9,10-dimethyl-tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 carbon number such as dodeca-4-ene having a 2 an alkyl group, ^6. 02, ^7] dodeca-4-enes; 9-vinyl tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 carbon number such as dodeca-4-ene having a 2 an alkenyl group, ^6. 02, ^7] dodeca-4-enes; 9-methylidene tetracyclo [6.2.1.13, ^6, 02, ^7] dodeca-4-ene, 9-ethylidene tetracyclo [6,2.1. 13, ⁶ . 02, ^7] tetracyclo [6.2.1.13 carbon number such as dodeca-4-ene has two less alkylidene group, ^6. 02, ^7] dodecamethylene-4-ene.
Preferred norbornene compounds (B) are tetracyclo [6.2.1.13, ⁶ . 02, ^7] dodecamethylene-4-ene.

  The preferred molar ratio [(a) / (b)] of the repeating unit (a) to the repeating unit (b) is in the range of (a) / (b) = 10/90 to 98/2, and more preferred molar The ratio [(a) / (b)] is in the range of 15/85 to 95/5, and the particularly preferred molar ratio [(a) / (b)] is in the range of 20/80 to 90/10. .

  The norbornene compound addition polymer in which the sum of the repeating unit (a) and the repeating unit (b) is usually 70 mol% or more of all the repeating units has the following repeating unit (c) of the norbornene compound monomer. May be.

[Repeating unit (c)]
The repeating unit (c) is composed of only carbon and hydrogen, and a part of the hydrogen of the norbornene compound monomer in which all the carbons are involved in the structure of the condensed ring skeleton is (1) the number of carbon atoms is 1. It is a repeating unit of a norbornene compound monomer having a structure substituted with only a functional group of ˜5 or (2) a functional group having 1 to 5 carbon atoms and a hydrocarbon group having 1 to 5 carbon atoms. Here, the functional group having 1 to 5 carbon atoms includes (1 ′) a functional group itself having 1 to 5 carbon atoms and (2 ′) hydrogen of a hydrocarbon group having 1 to 5 carbon atoms. And a tomb having a structure substituted with a group having 1 to 5 carbon atoms, and a hydrogen having a total carbon number of 1 to 5 and (3 ′) a functional group having 1 to 5 carbon atoms, This is a concept including a group having a structure substituted with 1 to 5 hydrocarbon groups and having 1 to 5 carbon atoms. A specific example of such a repeating unit (c) is a repeating unit represented by the general formula (5).

In General Formula (5), R ^{7 to} R ¹⁰ are a hydrogen atom, a functional group having 1 to 5 carbon atoms, or a hydrocarbon group having 1 to 5 carbon atoms, and at least one of R ^{7 to} R ^10. One is a functional group having 1 or 2 carbon atoms. k is an integer of 0-2.
Specific examples of the functional group having 1 to 5 carbon atoms include hydroxyl group, mercapto group, amino group, methoxy group, ethoxy group, methoxycarbonyl group, acetoxy group, epoxyethyl group, acetyl group, cyano group, hydroxymethyl group, hydroxy group An ethyl group, an N-methylamino group, an N-ethylamino group, an N, N-dimethylamino group, a methylthio group, and an ethylthio group.
The hydrocarbon group having 1 to 5 carbon atoms is the same as R ^{3 to} R ^{6 in} the general formula (3).

  The repeating unit (c) is obtained by addition polymerization of the norbornene compound (C) represented by the general formula (6).

Here, R ⁷ to R ¹⁰ and k are the same as R ⁷ to R ¹⁰ and k in the general formula (5).

Specific examples of the norbornene compound (C) include norbornenes having an alkoxy group having 1 to 5 carbon atoms such as 5-methoxy-2-norbornene, 5-ethoxy-2-norbornene, and 5,6-dimethoxy-2-norbornene. Norbornenes having a methoxycarbonyl group such as 5-methoxycarbonyl-2-norbornene and 5-methyl-5-methoxycarbonyl-2-norbornene; norbornenes having an acetoxy group such as 5-acetoxy-2-norbornene; Norbornenes having an epoxyethyl group such as epoxyethyl-2-norbornene; norbornenes having an acetyl group such as 5-acetyl-2-norbornene; 5-cyano-2-norbornene, 5-methyl-5-cyano-2- Norbornenes having a cyano group such as norbornene; 5- ( , N-dimethylamino) -2-norbornene and other norbornenes having an N, N-dimethylamino group; 5-methylthio-2-norbornene, 5-ethylthio-2-norbornene and the like alkyl thio groups having 1 to 5 carbon atoms Norbornenes having 9; methoxytetracyclo [6.2.1.13, ⁶ . 02, ^7] dodeca-4-ene, 9-ethoxy tetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, 9,10-dimethoxy-tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 carbon number such as dodeca-4-ene having 1-5 alkoxy groups, ^6. 02, ^7] dodeca-4-enes; 9-methoxycarbonyltetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, 9-methyl-9-methoxycarbonyltetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 having methoxycarbonyl group such dodeca-4-ene, ^6. 02, ^7] dodeca-4-enes; 9-acetoxy tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 having acetoxy groups such as dodeca-4-ene, ^6. 02, ^7] dodeca-4-enes; 9-epoxy-ethyl tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 having an epoxy ethyl group such as dodeca-4-ene, ^6. 02, ^7] dodeca-4-enes; 9-acetyl tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 having an acetyl group such as dodeca-4-ene, ^6. 02, ^7] dodeca-4-enes; 9-cyano-tetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, 9-methyl-9 cyano tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 having a cyano group such as dodeca-4-ene, ^6. 02, ^7] dodeca-4-enes; 9- (N, N- dimethylamino) - tetracyclo [6.2.1.13, ^6. 02, ^7] N, such as dodeca-4-ene, tetracyclo with N- dimethylamino group [6.2.1.13, ^6. 02, ^7] dodeca-4-enes; 9-methyl-thio tetracyclo [6.2.1.13, ^6. 02, ^7] dodeca-4-ene, 9-ethyl-thio tetracyclo [6.2.1.13, ^6. 02, ^7] tetracyclo [6.2.1.13 carbon number such as dodeca-4-ene having 1-5 alkylthio group, ^6. 02, ⁷ ] dodec-4-enes.

The carbon number of the functional group of the repeating unit (c) is 2 or less.
The ratio of the repeating unit (c) copolymerized with the norbornene compound addition polymer is usually 30 mol% or less of the total repeating units, and a preferable ratio is 10 mol% or less.

[Production of norbornene compound addition polymer]
The norbornene compound (A) represented by the general formula (2) and / or the norbornene compound (B) represented by the general formula (4) is an essential component, and is represented by the general formula (6) as necessary. A norbornene compound monomer mixture containing the norbornene compound (C) is subjected to addition polymerization in the presence of a polymerization catalyst to obtain a norbornene compound addition polymer.

  The polymerization catalyst for obtaining the norbornene compound addition polymer is not particularly limited. Specific examples of the polymerization catalyst include polymerization catalysts such as [6-methoxynorbornene-2-yl-5-palladium (cyclooctadiene)] hexafluorophosphate described in JP-A No. 11-505880; International Publication No. 2000 / Polymer catalyst such as (allyl) palladium chloride dimer / tricyclohexylphosphine / lithium tetrakis (pentafluorophenyl) borate / 2.5 ether described in pamphlet of No. 20472; (phenyl) palladium bis (tri) described in JP-A-2001-098035 Polymerization catalysts such as phenylphosphine) iodide / methylaluminoxane; Group 10 transition metal catalysts.

The norbornene compound addition polymer obtained by the above method may have an olefinically unsaturated bond, but a polymer in which this olefinically unsaturated bond is hydrogenated is also included in the cyclic olefin addition polymer of the present invention. .
The hydrogenation reaction is carried out by a generally known method, that is, by contacting hydrogen and a norbornene compound addition polymer in the presence of a hydrogenation catalyst. Specific examples of the hydrogenation catalyst include a group 8-10 transition metal such as nickel, palladium, platinum, cobalt, ruthenium, rhodium or a compound thereof supported on a porous carrier such as carbon, alumina, silica, silica alumina, and diatomaceous earth. A solid catalyst; a group 4-10 metal carboxylate of cobalt, nickel, palladium, etc .; a combination of β-diketone compound with organoaluminum or organolithium; a homogeneous catalyst of a complex of ruthenium, rhodium, iridium, etc. is there.

After the addition polymerization reaction and / or hydrogenation reaction, the catalyst is preferably removed. Specific examples of catalyst removal methods include adsorption removal with an adsorbent such as silica, alumina, activated carbon, etc .; removal with an ion exchange resin; filtration of the catalyst residue insolubilized with a chelating agent; and a large amount of polymer solution. This is a method of solidifying by adding to a poor solvent such as methanol or acetone.
Specific examples of the recovery of the norbornene compound addition polymer after the addition polymerization reaction include a method of directly removing the solvent from the polymer solution and a method of coagulation and separation with a poor solvent such as methanol.

  The polystyrene-converted weight average molecular weight (Mw) of the cyclic olefin addition polymer used in the present invention, as measured by gel permeation chromatography, is usually 50,000 to 1,000,000, and more preferable Mw is 70,000 to 800,000. When Mw is lower than 50,000, the mechanical properties are inferior, and when Mw is higher than 1,000,000, the solution viscosity becomes high and handling may be difficult. The number average molecular weight (Mn) of the cyclic olefin addition polymer used in the present invention is preferably 10,000 to 600,000, and particularly preferably Mn is 50,000 to 400,000. The glass transition temperature of the cyclic olefin addition polymer used in the present invention is usually 235 to 400 ° C, preferably 235 to 300 ° C. The resin composition obtained when it exists in this range is excellent in heat resistance.

(Lubricant)
In the present invention, a lubricant having a 5% heating weight loss temperature of 300 ° C. or higher under a nitrogen atmosphere is selected from commonly available lubricants and used. The upper limit of the 5% heating weight loss temperature of the lubricant under a nitrogen atmosphere is usually 450 ° C. or lower. Transparency of a molded article obtained by melt-molding a resin composition containing a lubricant having a 5% heating weight loss temperature of less than 300 ° C. and a cyclic olefin addition polymer in a nitrogen atmosphere is not sufficiently high.
The type of lubricant used in the present invention is not particularly limited. Hydrocarbon lubricants, fatty acid amide lubricants, ester lubricants, alcohol lubricants, fatty acid lubricants, metal soap lubricants are used as lubricants used in the present invention. These may be used alone or in combination of two or more.
From the viewpoint of improving the transparency of the molded article of the present invention, preferable lubricants are hydrocarbon lubricants and ester lubricants, and more preferable lubricants are hydrocarbon lubricants.

The hydrocarbon-based lubricant is a low molecular weight polyolefin having an olefin as a basic structural unit and a weight average molecular weight of 500 to 10,000. Specific examples of the hydrocarbon lubricant are liquid paraffin, microcrystalline wax, paraffin wax, polyethylene wax, polypropylene wax, ethylene / vinyl acetate copolymer wax, and polyolefin ionomer wax.
From the viewpoint of improving the transparency of the molded article of the present invention, a lubricant composed only of hydrocarbon is preferred, and microcrystalline wax and paraffin wax are more preferred.
Specific examples of the available paraffin wax are FNP0115 (5% weight reduction temperature: 401 ° C., manufactured by Nippon Seiwa Co., Ltd.), LUVAX1211 (5% weight reduction temperature: 349 ° C., manufactured by Nippon Seiwa Co., Ltd.). is there.
A specific example of the available microcrystalline wax is Hi-Mic-1090 (5% weight loss temperature: 370 ° C., manufactured by Nippon Seiwa Co., Ltd.).

  The ester lubricant is a compound having 10 to 200 carbon atoms having two or more ester bonds in the molecule. Specific examples of ester lubricants include pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol distearate, glycerol dilaurate, glycerol tristearate, trimethylolpropane distearate, glycerol distearate, glycerol tribehe , Pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, dipentaerythritol tetrastearate, dipentaerythritol distearate, dipentaerythritol dibehenate, trimethylolpropane tricaplate, trimethylolpropane It is an ester of a higher carboxylic acid such as diolate and a polyhydric alcohol. These lubricants can be used alone or in combination of two or more. The lubricant is preferably contained in an amount of 0.5 to 15 parts by mass, more preferably 0.5 to 10 parts by mass, and further preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the cyclic olefin addition polymer. Has been.

(Glass transition temperature of resin composition)
The glass transition temperature of the resin composition used in the present invention is 230 to 400 ° C, preferably 230 to 300 ° C. The heat resistance of a molded product obtained by melt-molding a resin composition having a glass transition temperature of less than 230 ° C. is not sufficiently high. On the other hand, if the glass transition temperature is too high, melt molding becomes difficult, or the molded product obtained by melt molding may be inferior in transparency due to burning or coloring deterioration. The glass transition temperature of the resin composition used in the present invention is appropriately adjusted depending on conditions such as the glass transition temperature of the cyclic olefin addition polymer, the type and amount of additives, and the like.

(Molding of resin composition)
The resin composition used in the present invention is melt-molded by a known melt-molding method to obtain the molded body of the present invention. Specific examples of the melt molding method are extrusion molding, injection molding, compression molding, vacuum molding, cast molding, and blow molding.

(Other additives)
When the molded product of the present invention is molded from a resin composition containing a cyclic olefin addition polymer and a lubricant, various additives may be blended as necessary. Specific examples of such additives include fillers, antioxidants, phosphors, ultraviolet absorbers, antistatic agents, light stabilizers, near infrared absorbers, colorants (dyes, pigments, etc.), plasticizers, flame retardants, It is a crosslinking agent.

Specific examples of the filler are oxides of metals such as silicon, titanium, aluminum, and zirconium.
Specific examples of the antioxidant are a phenolic antioxidant, a lactone antioxidant, a phosphorus antioxidant, and a thioether antioxidant.
The phosphor is excited by receiving light and emits light having a wavelength longer than the excitation wavelength. For example, when the optical element is sealed, the phosphor is used for receiving a wavelength in the ultraviolet region from a blue region where the optical element emits light and emitting a wavelength in the visible region.
The method for blending these additives is not particularly limited.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, the evaluation method will be described.

Evaluation in this example is performed by the following method.
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
The molecular weight of the polymer was determined as a standard polystyrene equivalent value by gel permeation chromatography (GPC) using chloroform as an eluent.
(2) Composition ratio of polymer The composition ratio of the polymer was determined by ¹ H-NMR measurement.
(3) Glass transition temperature (Tg)
The glass transition temperature of the resin composition was determined from the temperature at the inflection point of the storage elastic modulus G ′ in the dynamic viscoelasticity measurement. The dynamic viscoelasticity measurement is performed by a strain control type viscoelasticity device (ARES, manufactured by Rheometric scientific), and a sample plate having a width of 10 mm, a length of 40 mm, and a thickness of 1 mm is measured with a measurement frequency of 10 rad / sec and a heating rate of 10 ° C. The temperature at the inflection point of the storage elastic modulus G ′ was measured under the condition of 0.1% strain.
(4) Total light transmittance The total light transmittance of an injection molded product having a thickness of 3 mm, a length of 40 mm, and a width of 40 mm is determined by a turbidimeter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7105. Measured.
(5) 5% weight loss temperature Simultaneous differential thermo-thermogravimetric measurement device (TG / DTA6300, manufactured by SII Nanotechnology) is used, and the heating rate is 10 ° C from 50 ° C to 500 ° C with a nitrogen flow rate of 350 ml / min. The temperature at which 5% of the initial weight of the lubricant was reduced under the conditions of / min was measured.

(Production Example 1)
1.54 parts by weight of (allyl) palladium (tricyclohexylphosphine) chloride and 2.28 parts by weight of lithium tetrakis [pentafluorophenyl] borate are placed in a nitrogen-substituted glass reactor, followed by 5 parts by weight of toluene. As a result, a catalyst solution was prepared.
Then, 1,430 parts by mass of 2-norbornene (hereinafter sometimes abbreviated as “NB”), 1,120 parts by mass of 5-ethyl-2-norbornene (hereinafter abbreviated as “ENB”), 420 parts by mass of styrene as a molecular weight regulator and 6,100 parts by mass of toluene as a polymerization solvent are charged into a pressure-resistant glass reactor equipped with a stirrer substituted with nitrogen, and the above catalyst solution is added to initiate polymerization, at 60 ° C. The reaction was carried out for 4 hours. After 5,000 parts by mass of toluene was added to the reaction solution, 400 parts by mass of hydrotalcite (KYOWARD 500SN, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, the reaction solution was introduced into an autoclave equipped with a stirrer, and hydrogen pressure The mixture was stirred for 6 hours under the conditions of 1 MPa and 200 ° C. The resulting polymer solution was suction filtered to remove hydrotalcite. The filtrate is poured into a large amount of methanol, and the addition polymer (A ′) is completely precipitated. The addition polymer (A ′) is filtered and washed, and then dried under reduced pressure at 80 ° C. for 18 hours. As a result, 2,240 parts by mass of an addition polymer (A ′) was obtained.
The weight average molecular weight (Mw) of the obtained addition polymer (A ′) is 201,000, and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 3.10, the composition ratio of the addition polymer (A ′) was NB / ENB = 61/39 (mol / mol). The glass transition temperature of the addition polymer (A ′) was 283 ° C.

(Example 1)
100 parts by mass of addition polymer (A ′), 4 parts by mass of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.), tetrakis- [methylene-3- (3 ′, 5′-ditertiary) as an antioxidant -Butyl-4′-hydroxyphenyl) propionate] 1 part by mass of methane (Irganox 1010, manufactured by Ciba Specialty Chemicals) was dissolved and dispersed in 700 parts by mass of toluene, and the resulting dispersion was subjected to a vacuum dryer. The solvent was removed at 200 ° C. overnight. Then, the obtained resin composition was press-molded under conditions of 300 ° C. under vacuum with a vacuum press machine (manufactured by Imoto Seisakusho Co., Ltd.). 20 parts by mass of the press-molded resin composition was kneaded for 2 minutes at 350 ° C. and 100 rpm with a small kneader (Compounder Micro15, manufactured by DSM Xplore), and then a small injection molding machine (Micro Injection Molding Machine 10cc). , Manufactured by DSM Xplore) under the conditions of a resin temperature of 350 ° C., a mold temperature of 200 ° C., and an injection pressure of 0.6 MPa, a molded body (A) having a length of 40 mm, a width of 40 mm, and a thickness of 3 mm was obtained. .
The molded product (A) was taken out from the mold without cracking, and the strength of the molded product (A) was sufficient. A test piece for measuring a glass transition temperature having a thickness of 1 mm obtained by compression-molding a part of the molded body (A) at 300 ° C. was obtained. The glass transition temperature and the total light transmittance of the molded body (A) were measured, and the results are shown in Table 1.

(Example 2)
In Example 1, the same operation as Example 1 was performed except that the amount of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.) was changed to 15 parts by mass, and a molded body (B) was obtained. .
The molded body (B) was taken out from the mold without cracking, and the strength of the molded body (B) was sufficient. The glass transition temperature of the resin composition constituting the molded body (B) and the total light transmittance of the molded body (B) were measured, and the results are shown in Table 1.

(Example 3)
In Example 1, the same operation as in Example 1 was performed except that paraffin wax (LUVAX 1211, manufactured by Nippon Seiwa Co., Ltd.) was used instead of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.). As a result, a molded body (C) was obtained.
The molded body (C) was taken out from the mold without cracking, and the strength of the molded body (C) was sufficient. The glass transition temperature of the resin composition constituting the molded body (C) and the total light transmittance of the molded body (C) were measured, and the results are shown in Table 1.

Example 4
Example 1 except that microcrystalline wax (Hi-Mic-1090, manufactured by Nippon Seiwa Co., Ltd.) was used in place of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.) in Example 1. The same operation was performed to obtain a molded body (D).
The molded body (D) was taken out from the mold without cracking, and the strength of the molded body (D) was sufficient. The glass transition temperature of the resin composition constituting the molded body (D) and the total light transmittance of the molded body (D) were measured, and the results are shown in Table 1.

(Example 5)
In Example 1, the same operation as in Example 1 was performed except that pentaerythritol distearate was used instead of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.). Obtained.
The molded body (E) was taken out from the mold without cracking, and the strength of the molded body (E) was sufficient. The glass transition temperature of the resin composition constituting the molded body (E) and the total light transmittance of the molded body (E) were measured, and the results are shown in Table 1.

(Example 6)
In Example 1, the same operation as in Example 1 was carried out except that dipentaerythritol dibehenate was used instead of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.), and the molded product (F) was gotten.
The molded body (F) was taken out from the mold without cracking, and the strength of the molded body (F) was sufficient. The glass transition temperature of the resin composition constituting the molded body (F) and the total light transmittance of the molded body (F) were measured, and the results are shown in Table 1.

(Comparative Example 1)
In Example 1, the same operation as Example 1 was performed except that paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.) was not added, and a molded body (G) was obtained.
The molded body (G) was broken when taken out from the mold, and the strength of the molded body (G) was not sufficient.
The glass transition temperature of the resin composition constituting the molded body (G) was measured, and the result is shown in Table 1. In addition, since the molded object (G) was cracked, the total light transmittance of the molded object (G) was not able to be measured.

(Comparative Example 2)
In Example 1, the same operation as in Example 1 was performed except that glycerin monostearate was used instead of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.) to obtain a molded body (H). It was.
The molded body (H) was taken out from the mold without cracking, and the strength of the molded body (H) was sufficient. The glass transition temperature of the resin composition constituting the molded body (H) and the total light transmittance of the molded body (H) were measured, and the results are shown in Table 1.

(Comparative Example 3)
In Example 1, the same operation as in Example 1 was performed except that glycerin mono-12-hydroxystearate was used instead of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.). I) was obtained.
The molded body (I) was taken out from the mold without cracking, and the strength of the molded body (I) was sufficient. The glass transition temperature of the resin composition constituting the molded body (I) and the total light transmittance of the molded body (I) were measured, and the results are shown in Table 1.

(Comparative Example 4)
In Example 1, the same operation as Example 1 was performed except that the amount of paraffin wax (FNP0115, manufactured by Nippon Seiwa Co., Ltd.) was changed to 20 parts by mass, and a molded body (J) was obtained. It was.
The molded body (J) was cracked when taken out from the mold, and the strength of the molded body (J) was not sufficient.
The glass transition temperature of the resin composition constituting the molded body (J) was measured, and the result is shown in Table 1. In addition, since the molded object (J) was broken, the total light transmittance of the molded object (J) could not be measured.

Although the glass transition temperature of the composition of the addition polymer (A ′) to which no lubricant is added is high, the molded article of Comparative Example 1 in which the composition is injection molded has sufficient strength to be taken out from the mold. Does not have.
The molded bodies of Comparative Examples 2 and 3 in which a resin composition containing a lubricant having a 5% weight loss temperature under a nitrogen atmosphere of less than 300 ° C. was injection molded did not have high total light transmittance. The transparency of the molded body is not high.
The molded body of Comparative Example 4 containing a large amount of a lubricant and injection-molded with a resin composition having a glass transition temperature of less than 230 ° C. does not have sufficient strength to be taken out from the mold.
Compared to the molded bodies of Comparative Examples 1 to 4, the molded body of the present invention has excellent transparency and heat resistance.

  The molded body of the present invention includes a color filter substrate, a light guide plate, a protective film, a deflection film, a retardation film, a touch panel, a transparent electrode substrate, an optical recording substrate (CD, MD, DVD, etc.), a TFT substrate, and a liquid crystal display substrate. It is suitably used as an optical component such as an organic EL display substrate, an optical waveguide, and a lens. Furthermore, the molded body of the present invention is also used as an electrical insulation component, an electrical / electronic component, an electronic component sealant, a medical device, and a packaging material.

Claims (4)

A molded article obtained by melt-molding a resin composition having a glass transition temperature of 230 to 400 ° C. containing a lubricant and a cyclic olefin addition polymer having a 5% weight loss temperature of 300 ° C. or higher under a nitrogen atmosphere. The molded object according to claim 1, wherein the lubricant is contained in an amount of 0.5 to 15 parts by mass with respect to 100 parts by mass of the cyclic olefin addition polymer. The molded article according to claim 1 or 2, wherein the lubricant is composed of a hydrocarbon. The molded product according to any one of claims 1 to 3, which is an optical component.