KR20080039800A - Process for producing a molded optical lens of thin configuration - Google Patents

Abstract

A method for manufacturing a thin molded optical lens is provided to allow a molded optical lens to be used for an optical lens constituting a small camera unit. A method for manufacturing a thin molded optical lens comprises the steps of injection-molding annular olefin-based resin and filling the annular olefin-based resin in a cavity of a molding device, and manufacturing a molded optical lens. The molded optical lens includes a flange section and a lens section, which are coupled with each other through a concave section. The flange section has a thickness of 0.5mm or less. The concave section has a thickness less than that of the flange section, and has a diameter of 10mm or less. The olefin-based resin is filled in the cavity at the speed of 2500mm/s to 20000mm/s at maximum.

Description

Manufacturing method of thin optical lens molded article {PROCESS FOR PRODUCING A MOLDED OPTICAL LENS OF THIN CONFIGURATION}

This invention relates to the manufacturing method of a thin optical lens molded object. More specifically, the present invention relates to a method for producing a thin optical lens molded article which is injection molded under specific conditions.

In recent years, due to the thinning of the main body of the cellular phone, the thinning of the camera lens module mounted in the cellular phone is also progressing. In thinning a camera lens module, the design which makes thin the thickness itself of the optical lens which is a component which comprises the module is performed.

Here, a transparent thermoplastic resin is used for the optical lens in terms of processability and design freedom, and in particular, a cyclic olefin resin is preferably used in terms of optical deformation and heat resistance (see Patent Documents 1 and 2, below). ).

[Patent Document 1] Japanese Patent Application Laid-Open No. 01-132626

[Non-Patent Document 1] Plastics, vol. 43, No. 7, P96, 1992

[Non-Patent Document 2] Functional Materials, vol. 14, No. 11, P51, 1994

However, when processing a thin optical lens molded body by injection molding using such cyclic olefin resin, there existed a problem that the optical distortion which generate | occur | produces inside an optical lens becomes large, or surface precision falls.

An object of the present invention is to solve the above problems, and to provide a method for producing a thin optical lens molded article having small optical deformation and excellent stability of surface accuracy.

As a result of earnestly researching to solve the above problems, the present inventors have found that when the molten resin is filled into the cavity at a specific speed, a thin optical lens molded article having small optical deformation and excellent stability of surface accuracy can be produced. The invention has been completed.

That is, the manufacturing method of the optical lens molded object which concerns on this invention,

The molten cyclic olefin resin is injected from the nozzle of the injection molding machine, the cavity of the mold apparatus is filled with the cyclic olefin resin,

A flange portion and a lens portion are joined via a concave portion, wherein the thickness of the flange portion is 0.5 mm or less, the thickness of the concave portion is 0.4 mm or less while being less than the thickness of the flange portion, and the optical lens molded body having a diameter of 10 mm or less. Way,

The filling is performed such that the value v _max at the highest speed among the speeds v of the cyclic olefin resin in the injection direction from the nozzle is 2500 to 20,000 mm / s.

It is preferable that the said cyclic olefin resin contains 1 or more types of polar groups.

According to the present invention, a thin optical lens molded article having small optical deformation and good surface accuracy is obtained. This optical lens molded body is useful as an optical lens constituting a compact camera unit such as a camera lens unit of a mobile phone or a camera unit of a personal computer.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In the manufacturing method of this invention, molten cyclic olefin resin is injected from the nozzle of an injection molding machine, the cyclic olefin resin is filled in the cavity of a metal mold | die apparatus, and the optical lens molded object which has a specific shape is obtained.

1. Cyclic olefin resin

As a cyclic olefin resin used for this invention, the (co) polymer which has a unit derived from the cyclic olefin compound represented by following General formula (1) is mentioned. This (co) polymer is obtained by superposing | polymerizing the monomer containing the said cyclic olefin compound.

(Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group or a polar group, and R ¹ and R ² , or R ³ and R ⁴ may be integrated to form a divalent organic group). R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic structure or a polycyclic structure, m represents 0 or a positive integer, and p represents 0 or a positive integer.

In Formula 1, R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having preferably 1 to 10, more preferably 1 to 4, particularly preferably 1 or 2 carbon atoms; It is more preferable that one of R <^2> and R <^4> is a hydrogen atom, and the other is a said monovalent polar group. In this case, as said hydrocarbon group represented by R <^1> or R <^3> , an alkyl group is preferable and a methyl group is especially preferable. Moreover, when one of R <^2> and R <^4> uses the cyclic olefin which is a polar group represented by following formula (2), the cyclic olefin resin which has high glass transition temperature and low hygroscopicity, and is excellent in adhesiveness with various materials is further It is preferable at the point obtained.

-(CH ₂ ) _n COOR

In the formula (2), R is preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 or 2 carbon atoms. Here, as said hydrocarbon group, an alkyl group is preferable. Moreover, since n is 0-5 normally and cyclic olefin with a small value of n is obtained, since cyclic olefin resin with a high glass transition temperature is obtained, cyclic olefin (-COOR) whose n is 0 is easy to synthesize | combine easily. Particularly preferred.

In particular, when R <^1> is an alkyl group, R <^2> is a polar group represented by the said Formula (2), and R <^3> and R <^4> is a hydrogen atom, it is preferable at the point from which a cyclic olefin resin with low hygroscopicity is obtained.

R ¹ and R ² , or R ³ and R ⁴ may be integrated to form a divalent organic group, and R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic structure or a polycyclic structure. .

m represents 0 or a positive integer, Preferably it represents the integer of 0-3. p represents 0 or a positive integer, Preferably it represents the integer of 0-3. Moreover, More preferably, m + p is an integer of 0-4, Especially preferably, m + p is an integer of 0-2. Most preferably m = 1 and p = 0. When cyclic olefin of m = 1 and p = 0 is used, cyclic olefin resin which is excellent also in mechanical strength while glass transition temperature is high is obtained.

The cyclic olefin represented by the formula (1) may be used alone, or may be used in combination of two or more thereof.

Although the following compounds can be specifically mentioned as said cyclic olefin, It is not limited to these compounds.

Bicyclo [2.2.1] hept-2-ene,

Tricyclo [4.3.0.1 ^2,5 ] -8-decene,

Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

^Pentacyclo [6.5.1.1 ^{3,6 2,7} .0 ^9,13 ] -4- ^pentadecene ,

5-methylbicyclo [2.2.1] hept-2-ene,

5-ethylbicyclo [2.2.1] hept-2-ene,

5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,

5-cyanobicyclo [2.2.1] hept-2-ene,

8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-ethylidenebicyclo [2.2.1] hept-2-ene,

8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-phenylbicyclo [2.2.1] hept-2-ene,

8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene,

5-fluorobicyclo [2.2.1] hept-2-ene,

5-fluoromethylbicyclo [2.2.1] hept-2-ene,

5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,

5,5-difluorobicyclo [2.2.1] hept-2-ene,

5,6-difluorobicyclo [2.2.1] hept-2-ene,

5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,

5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,

5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,

5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,

5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,

5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,

8-fluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-difluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

(Ethoxycarbonyl 2,2,2-trifluoroethyl) 8-methyl-8 and the like can be mentioned tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene.

Specifically as a (co) polymer obtained by superposing | polymerizing the monomer containing the said cyclic olefin compound,

(1) a ring-opening polymer of a cyclic olefin represented by the formula (1),

(2) a ring-opening copolymer of a cyclic olefin represented by the formula (1) and a copolymerizable monomer,

(3) hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above,

(4) a hydrogenated (co) polymer after cyclization of the ring-opening (co) polymer of (1) or (2) by a Friedel Crafts reaction,

(5) a saturated copolymer of a cyclic olefin represented by the formula (1) and an unsaturated double bond-containing compound,

(6) an addition type (co) polymer of a cyclic olefin represented by the formula (1) and at least one monomer selected from vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and hydrogenated (co) polymers thereof;

(7) The alternating copolymer of cyclic olefin and acrylate represented by the said Formula (1) is mentioned.

(1) ring-opening polymer and (2) ring-opening copolymer

The ring-opening polymer (1) and the ring-opening copolymer (2) are obtained by ring-opening polymerization of the cyclic olefin or ring-opening copolymerization of the cyclic olefin with a copolymerizable monomer in the presence of a metathesis catalyst.

<Copolymerizable monomer>

Cycloolefin is mentioned as said copolymerizable monomer, Preferably carbon number is 4-20, More preferably, cycloolefin of 5-12 is preferable. More specifically, cyclobutene, cyclopentene, cycloheptene, cyclooctene, dicyclopentadiene, etc. are mentioned. These cycloolefins may be used individually by 1 type, and may use 2 or more types together.

The use ratio of the cyclic olefin and the copolymerizable monomer is preferably 100/0 to 50/50, more preferably 100/0 to 60/40 in terms of weight ratio (cyclic olefin / copolymerizable monomer). On the other hand, "cyclic olefin / copolymerizable monomer = 100/0" means the case of superposing | polymerizing a cyclic olefin.

<Catalyst for Ring Opening Polymerization>

The metathesis catalyst used in the ring-opening (co) polymerization reaction is a catalyst containing a combination of the following compound (a) and compound (b).

(a) at least one compound selected from compounds of W, Mo and Re.

(b) Deming Periodic Table Group IA elements (e.g., Li, Na, K, etc.), Group IIA elements (e.g., Mg, Ca, etc.), Group IIB elements (e.g., Zn, Cd, Hg, etc.) ), One or more selected from Group IIIA elements (e.g., B, Al, etc.), Group IVA elements (e.g., Si, Sn, Pb, etc.) and Group IVB elements (e.g., Ti, Zr, etc.) At least one compound selected from the group consisting of compounds containing an element and at least one bond of carbon and one or more bonds of the element and hydrogen.

In addition, the metathesis catalyst may include an additive (c) described later to increase its activity.

Specific examples of the compound _{(a), WCl 6, MoCl} 6, ReOCl 3 , such as the Japanese Unexamined Patent Publication (Kokai) No. 1-132626 eighth page compounds described in Haran left the page to the right of line 86 line 17 sangran Can be mentioned.

Specific examples of the compound (b) include nC ₄ H ₉ Li, (C ₂ H ₅ ) ₃ Al, (C ₂ H ₅ ) ₂ AlCl, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlCl ₂ , methylalumoxane, LiH, etc. The compound of Unexamined-Japanese-Patent No. 1-32626 (8th page upper right column 18th line-8th page right lower column 3rd line) is mentioned.

As the additive (c), alcohols, aldehydes, ketones, amines, and the like can be preferably used, and the right side of the eighth page of Japanese Patent Laid-Open No. Hei 132626 is the 16th to the bottom of the ninth page. The compound described in the column 17 of the column may be used.

The ratio of the compound (a) and the compound (b) is usually 1: 1 to 1:50, preferably 1: 2 to 1:30 in the metal atomic ratio [(a) :( b)].

The ratio of the additive (c) and the compound (a) is usually 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 in a molar ratio [(c) :( a)].

The metathesis catalyst is used in an amount such that the molar ratio [(a): cyclic olefin] of the compound (a) and the cyclic olefin is usually 1: 500 to 1: 50,000, preferably 1: 1,000 to 1: 10,000.

<Solvent for Polymerization Reaction>

In the ring-opening (co) polymerization reaction, the solvent is used as a solvent constituting the molecular weight regulator solution described later, or a solvent of a cyclic olefin and / or a metathesis catalyst. As such a solvent, For example, Alkanes, such as a pentane, hexane, heptane, an octane, a nonane, decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibromide, chloroform and tetrachloroethylene; Aryl halides such as chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate; Ethers such as dibutyl ether, tetrahydrofuran, dimethoxyethane and the like. These solvents can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.

The amount of the solvent used is preferably an amount such that the weight ratio (solvent: cyclic olefin) of the solvent and the cyclic olefin is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.

<Molecular weight regulator>

Although the molecular weight of the ring-opening (co) polymer obtained can be adjusted by polymerization temperature, the kind of catalyst, and the kind of solvent, it can also adjust by coexisting a molecular weight modifier.

As a preferable molecular weight modifier, alpha olefins and styrene, such as ethylene, a propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, are mentioned, for example. Among them, 1-butene and 1-hexene are particularly preferred. In addition, these molecular weight modifiers can be used individually or in mixture of 2 or more types.

The use amount of the molecular weight modifier is usually 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, based on 1 mol of the cyclic olefin provided in the ring-opening polymerization reaction.

Although the said ring-opening copolymer can be obtained by ring-opening copolymerizing a cyclic olefin and a copolymerizable monomer, Furthermore, conjugated diene compounds, such as polybutadiene and polyisoprene, a styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene Cyclic olefins can also be ring-opened copolymerized in the presence of an unsaturated hydrocarbon-based polymer containing two or more carbon-carbon double bonds in the main chain thereof.

(3) hydrogenated (co) polymers

Although the said ring-opening (co) polymer can be used as it is, the hydrogenation (co) polymer (3) obtained by further hydrogenating here is useful as resin excellent in impact resistance.

The hydrogenation reaction is a conventional method, i.e., a hydrogenation catalyst is added to a solution containing a ring-opening (co) polymer, and hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm is 0 to 200 deg. Preferably, the reaction can be carried out at 20 to 180 ° C.

<Hydrogenated Catalyst>

As said hydrogenation catalyst, the catalyst used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are mentioned.

As a heterogeneous catalyst, the solid catalyst which supported noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickelacetylacetonate / triethylaluminum, cobalt acid / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine Rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of these catalysts may be powder or granular.

These hydrogenated catalysts are preferably used in a ratio such that the weight ratio (opening (co) polymer: hydrogenated catalyst) of the ring-opening (co) polymer and the hydrogenation catalyst is 1: 1 × 10 ⁻⁶ to 1: 2.

The hydrogenated (co) polymer (3) has excellent thermal stability, and its properties do not deteriorate even when heated during molding processing or when used as a product.

The hydrogenation rate of the hydrogenated (co) polymer (3) is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably the value measured under the condition of 500 MHz by ¹ H-NMR. Is 98% or more, most preferably 99% or more. As the hydrogenation rate is higher, molded articles such as light guides having excellent stability to heat and light and having stable characteristics over a long period of time can be obtained.

Moreover, it is preferable that gel content of the said hydrogenated (co) polymer (3) is 5 weight% or less, and it is especially preferable that it is 1 weight% or less.

(4) hydrogenated (co) polymers

Hydrogenated (co) polymer (4) is obtained by cyclizing the ring-opened (co) polymer of (1) or (2) by a Friedel Crafts reaction, followed by hydrogenation.

The method of cyclizing the ring-opening (co) polymer by the Friedel Crafts reaction is not particularly limited, and for example, a known method using an acidic compound described in JP-A-50-154399 can be adopted. .

Specific examples of the acidic compound include Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite and activated clay, and Bronsted acid.

The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the hydrogenation reaction of the above (3).

(5) saturated copolymer

The saturated copolymer (5) is obtained by addition polymerization of an unsaturated double bond-containing compound to the cyclic olefin in the presence of an addition polymerization catalyst. The addition polymerization method can apply a conventionally well-known method.

<Unsaturated double bond containing compound>

As an unsaturated double bond containing compound, olefin type compounds, such as ethylene, propylene, butene, are mentioned, for example, Among these, an olefin type compound of carbon number preferably 2-12, More preferably, 2-8 is preferable. Do.

The amount of the unsaturated double bond-containing compound is preferably 90/10 to 40/60 in terms of the weight ratio of the cyclic olefin and the unsaturated double bond-containing compound (cyclic olefin / unsaturated double bond-containing compound), and 85/15 to 50/50. This is more preferable. However, the total weight of a cyclic olefin and an unsaturated double bond containing compound shall be 100.

<Addition polymerization catalyst>

As addition polymerization catalyst, the combination of the at least 1 sort (s) of compound chosen from a titanium compound, a zirconium compound, and a vanadium compound, and an organoaluminum compound as a crude catalyst is mentioned.

Titanium tetrachloride, titanium trichloride, etc. are mentioned as said titanium compound, Bis (cyclopentadienyl) zirconium chloride, bis (cyclopentadienyl) zirconium dichloride, etc. are mentioned as a zirconium compound, As a vanadium compound, a chemical formula VO ( OR) _a X _b or V (OR) _c X _d [where R is a hydrocarbon group, X is a halogen atom, 0≤a≤3, 0≤b≤3, 2≤ (a + b) ≤3, 0≤ c ≤ 4, 0 ≤ d ≤ 4, 3 ≤ (c + d) ≤ 4] or an electron donating adduct thereof.

Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes, and nitrogen such as ammonia, amines, nitriles, and isocyanates. Containing electron donors and the like.

Examples of the organoaluminum compound include compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond. The said organoaluminum compound may be used independently and may use 2 or more types together.

The ratio of the amount of the compound used in the titanium compound, the zirconium compound and the vanadium compound (when two or more are used in combination) to the amount of the organoaluminum compound used is the ratio of the aluminum atom to the titanium atom or the like (Al / Ti, etc.) Furnace is usually 2 or more, preferably 2 to 50, particularly preferably 3 to 20.

As a solvent used by the said addition polymerization reaction, the solvent illustrated by the said ring-opening (co) polymerization reaction is mentioned.

In addition, molecular weight control of the saturated copolymer (5) can be normally performed using hydrogen.

(6) addition type (co) polymers and hydrogenated (co) polymers thereof

The addition type (co) polymer (6) is obtained by addition polymerization of at least one monomer selected from vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers to the cyclic olefins.

<Vinyl cyclic hydrocarbon monomer>

As said vinyl-type cyclic hydrocarbon type monomer, For example, Vinyl cyclopentene type monomers, such as 4-vinyl cyclopentene and 2-methyl- 4-isopropenyl cyclopentene; Vinylated 5-membered ring hydrocarbon monomers such as vinylcyclopentane monomers such as 4-vinylcyclopentane and 4-isopropenylcyclopentane; Vinyl such as 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene Cyclohexene monomers; Vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane; Styrene monomers such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene; terpene monomers such as d-terpene, 1-terpene, diterpene, d-limonene, 1-limonene, and dipentene; Vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene; And vinylcycloheptane monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane. Among these monomers, styrene and α-methylstyrene are preferable. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

<Cyclopentadiene monomers>

As said cyclopentadiene type monomer, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-methylcyclopenta Dienes and the like. Among these monomers, cyclopentadiene is preferred. In addition, these monomers may be used individually by 1 type, and may use 2 or more types together.

The addition polymerization reaction can be carried out in the same manner as the addition polymerization reaction in the above (5).

Hydrogenation (co) polymer of the said addition type (co) polymer (6) can be obtained by hydrogenating the said addition type (co) polymer (6) by the method similar to said (3).

(7) alternating copolymer

The alternating copolymer (7) is obtained by radical polymerization of the cyclic olefin and acrylate in the presence of Lewis acid or the like.

<Acrylate>

As said acrylate, For example, C1-C20 linear, branched, or cyclic alkylacrylate, such as methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate; Heterocyclic group-containing acrylates having 2 to 20 carbon atoms such as glycidyl acrylate and 2-tetrahydrofurfuryl acrylate; Aromatic ring-containing acrylates having 6 to 20 carbon atoms such as benzyl acrylate; And acrylates having a polycyclic structure having 7 to 30 carbon atoms such as isoboroyl acrylate and dicyclopentanyl acrylate.

As for the ratio of the said cyclic olefin and an acrylate, these sum totals 100 mol, and 30-70 mol of cyclic olefins, 70-30 mol of acrylates are preferable, Preferably 40-60 mol of cyclic olefins, 60-60 acrylates 40 moles, particularly preferably 45 to 55 moles of cyclic olefins and 55 to 45 moles of acrylate.

The amount of Lewis acid used is preferably 0.001 to 1 mole based on 100 moles of acrylate.

It is also possible to use known organic peroxides or azobis radical polymerization initiators which generate free radicals.

The polymerization reaction temperature is usually -20 deg. C to 80 deg. C, preferably 5 deg. C to 60 deg. Moreover, the solvent illustrated by the said ring-opening (co) polymerization reaction is mentioned as a solvent for polymerization reactions.

On the other hand, the "alternative copolymer" in the present invention means that the structural units derived from cyclic olefins are not adjacent to each other, that is, the structural units derived from acrylate are bonded to the neighbors of the structural units derived from cyclic olefins. Means a copolymer. However, structural units derived from acrylate may be present adjacent to each other.

The intrinsic viscosity [η _inh ] of the cyclic olefin resin used in the present invention is preferably 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g. In addition, it is measured by gel permeation chromatography (GPC, column: TSKgel G7000HXL × 1, TSKgel GMHXL × 2, and TSKgel G2000HXL × 1 in series) using tetrahydrofuran as a solvent. The molecular weight of polystyrene is preferably a number average molecular weight (Mn) of 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and a weight average molecular weight (Mw) of preferably 20,000 to 300,000, More preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

Cyclic olefin resins having an intrinsic viscosity [η _inh ], a number average molecular weight (Mn) and a weight average molecular weight (Mw) in the above ranges have excellent molding processability, and according to this resin, heat resistance, water resistance, chemical resistance and mechanical properties This excellent molded article is obtained.

Moreover, the glass transition temperature (Tg) of the said cyclic olefin resin is 120 degreeC or more normally, Preferably it is 120-350 degreeC, More preferably, it is 120-250 degreeC, Especially preferably, it is 130-200 degreeC. The cyclic olefin resin having a Tg in the above range is hardly deformed even in the secondary processing involving the use under high temperature conditions or heating such as coating and printing, and has excellent molding processability and deterioration due to heat during molding processing. Difficult to do

In the present invention, a cyclic olefin resin having an index constant n of 0.3 or more and 0.5 or less is used when the melt viscosity is represented by a modified cross model represented by the following formula (1).

On the other hand, a thermoplastic resin is generally a non-Newtonian fluid whose apparent viscosity changes with shear rate. Several rheological models have been proposed to describe the viscosity characteristics of such non-Newtonian fluids, but the modified cross model defined by Equation 1 is used herein.

The cyclic olefin resin used in the present invention is characterized by a large change in the melt viscosity with respect to the shear rate. This characteristic is expressed by the value of the exponent constant n in the above formula (1), and the larger the value of n, the larger the change in the melt viscosity with respect to the shear rate.

N is 0.3 or more and 0.5 or less of cyclic olefin resin used for this invention. If n is less than 0.3, when the fluidity at the thin part is insufficient at the time of injection molding, and when the surface precision of the lens is included in the optical design, local deformation occurs at the thick part serving as the lens part and the burr at the flow end ( The occurrence of burr may occur. In addition, when n exceeds 0.5, the filling pressure in the lens mold cavity may be insufficient, and it may be remarkably difficult to maintain the surface accuracy of the lens. Therefore, cyclic olefin resin whose n is in the said range is used preferably for manufacture of the thin optical lens which has the above shapes.

It is preferable that the cyclic olefin resin used for this invention removes the dissolved water and oxygen component by a well-known method before injection molding. At this time, well-known drying apparatuses, such as a hot air dryer, a dehumidification dryer, a nitrogen circulation dryer, a dehumidification nitrogen circulation dryer, and a vacuum dryer, are used. Among these drying apparatuses, it is preferable to use a dryer which circulates an inert gas such as a reduced pressure dryer or nitrogen, since a molded article having color uniformity is easily obtained.

Although drying temperature and drying time are not specifically limited, Usually, it dries normally for 2 to 6 hours at Tg-100 degreeC-Tg-20 degreeC.

2. Optical lens molded body

In the optical lens of the present invention, the flange portion and the lens portion are coupled through the concave portion, and the diameter is 10 mm or less. It is preferable that the said diameter is 2 mm or more.

5 is an external view of a lens unit viewed in a vertical direction in the optical lens of the present invention. As shown in Fig. 5, the optical lens of the present invention has a flange portion, a recessed portion, and a lens portion serving as an optical path of light. On the other hand, the flange portion refers to the portion for holding the lens, which is provided outside the lens portion, it can be used for holding the lens portion, fixing the lens at the time of assembly, maintaining the lens spacing. The concave portion refers to a thin portion between the flange portion and the lens portion. In addition, the said diameter means the diameter of this circle, when supplementing an optical lens with a dotted line as a circle like FIG.

The cross-sectional shape of the optical lens is not particularly limited, and as illustrated in FIGS. 6A to 6F, may be spherical, aspherical, concave, convex, or the like. 6A to 6F are cross-sectional views along the line A in FIG. 5.

In addition, the optical lens of the present invention has a thickness of 0.5 mm or less for the flange portion, and a thickness of the concave portion of 0.4 mm or less while being below the thickness of the flange portion. In the optical lens of the present invention, the flange portion preferably has a thickness of 0.05 mm or more and 0.5 mm or less, and the recess portion has a thickness of 0.03 mm or more and 0.4 mm or less while being less than or equal to the thickness of the flange portion. Here, the thickness of the flange means a value measured at the position of the lens end. The concave portion is located between the lens portion and the flange portion, and is thinner than the flange portion when viewed from the flange portion toward the lens portion. The said recessed part means the value measured in the position where the thickness of the thin part becomes the thinnest.

The maximum value of the lens portion thickness is preferably 0.8 mm or less. This thin optical lens is also thin in the flange portion and the concave portion. Therefore, according to the optical lens of the present invention, since the thickness of the lens unit can be reduced, it is effective for thinning a camera device mounted on a cellular phone or the like.

3. injection molding

In the present invention, the molten cyclic olefin resin is injected from the nozzle of the injection molding machine, and the cavity of the mold apparatus having the space portion corresponding to the optical lens molded body is filled in the cyclic olefin resin. It is characterized by filling a resin. That is, the filling is performed so that the value v _max at the highest speed among the speeds v of the cyclic olefin resin in the injection direction from the nozzle is 2500 to 20,000 mm / s. Further, the value v _max at the highest speed among the speeds v is preferably 3000 mm / s to 15000 mm / s, particularly preferably 4000 mm / s to 12000 mm / s. This speed v is calculated as follows when the diameter of the cylinder of the injection molding machine used is Dc (mm), the injection speed is v _i (mm / s) and the diameter of the nozzle is Dn (mm).

v = (Dc / Dn) ² × v _i

If the value v _max at the fastest speed among the speeds v is less than 2500 mn / s, local optical deformation may occur in the effective surface of the optical lens molded body, and if it exceeds 20000 mm / s, the surface precision of the optical lens molded body may be inferior. At the same time, a flow mark can occur.

On the other hand, in shaping the lens, for the purpose of jetting prevention, burr prevention, and the like, in the initial stage (when passing through the gate) or the final stage of cavity filling, the value of the speed v is made smaller than 2500 mm / s. Technology can be used. That is, a technique for lowering the injection speed at the beginning or later stage of the molding can be used, but this does not impair the technique of the present invention. In this case, normally, when the lens portion and the flange portion of the cavity are filled, the speed v takes the value v _max at the fastest speed, and v _max is in the above range. In addition, when it is not necessary to make small the value of the speed v at the time of cavity filling, while the said speed v at the time of filling is constant, the speed v may be in the range of 2500-20000 mm / s.

Although the metal mold | die apparatus used for this invention is not specifically limited, The metal mold | die apparatus which has a gate shape shown below can be used preferably. In this mold apparatus, as shown in Fig. 1A, the cavity and the gate are coupled through the gate opening. The cavity has a shape corresponding to the optical lens molded body, and has a space corresponding to each of the flange portion, the recessed portion, and the lens portion of the optical lens molded body. In the mold apparatus, the gate is joined to a cavity and a runner (not shown).

As shown in Fig. 1 (b), in the mold apparatus for use in the present invention, the flange portion of the height direction of the cavity, the gate thickness t ₁ of the said gate opening and the height direction of the cavity at the gate opening It is preferable that the thickness t ₂ of satisfies the following expression (3).

t ₂ × 0.1≤t ₁ ≤t ₂ × 0.8

If t ₁ is smaller than t ₂ × 0.1, the surface precision of the optical lens molded body may be degraded, and if t ₁ is larger than t ₂ x 0.8, local optical deformation may occur in the optical lens molded body.

As shown in FIG. 2, the inclination angle of which one side of the height direction of the cavity is narrowed and narrowed in the width direction while both sides of the width direction of the cavity are equally narrowed toward the gate opening. It is preferable that α and the inclination angle β narrowing in the height direction satisfy the following equations (4) and (5), respectively.

30 ° ≤α≤60 °

20 ° ≤β≤60 °

If α is smaller than 30 °, local optical deformation may occur in the optical lens molded body, and if α is larger than 60 °, the surface accuracy of the optical lens molded body may be deteriorated and flow marks may occur. In addition, when β is smaller than 20 °, local optical deformation may occur in the optical lens molded body, and when β is larger than 60 °, the surface precision of the optical lens molded body may be deteriorated and flow marks may be generated.

In addition, as shown in FIG. 3, one side in the height direction of the cavity is narrowed and widened in the width direction while both sides of the width direction of the cavity are equally widened toward the gate opening. It is preferable that the inclination angle α and the inclination angle β narrowing in the height direction satisfy the following equations (6) and (7), respectively.

30 ° ≤α≤60 °

20 ° ≤β≤60 °

If α is smaller than 30 °, local optical deformation may occur in the optical lens molded body, and if α is larger than 60 °, the surface accuracy of the optical lens molded body may be deteriorated and flow marks may occur. When β is smaller than 20 °, local optical deformation may occur in the optical lens molded body, and when β is larger than 60 °, the surface precision of the optical lens molded body may be deteriorated and flow marks may occur.

In addition, as shown in FIG. 4, the gate has a flat portion, is coupled to the cavity through the flat portion, and the length L of the flat portion is preferably 0.2 to 2.0 mm.

When L is less than 0.2 mm, the effect of reducing local optical deformation becomes difficult to be obtained. When L exceeds 2.0 mm, surface precision is lowered and flow marks are more likely to occur.

In addition, the molded article (optical lens molded article) obtained by this invention is manufactured using the metal mold | die apparatus which has a well-known material. As a preferable material of a metal mold | die apparatus, normal carbon steel, stainless steel, or well-known alloys based on these are mentioned, The surface of a metal mold | die apparatus is a well-known coating process by quenching, chromium, titanium, diamond, etc., or Metal plating for pattern processing by a nickel type metal, a copper alloy, etc. can be performed.

In addition, when the pattern is formed on the surface of the molded article for the purpose of condensing or preventing reflection, the pattern is directly applied to a metal coating surface or metal plating surface of the mold apparatus or a stamper surface by a known processing machine such as an electric discharge machine or a cutting machine. It may form, or a pattern may be formed by methods, such as electroforming.

Further, in injection molding, a gas vent is provided around the cavity of the lens for the purpose of preventing carbonization of the resin resulting from high temperature by compression of the gas component in the mold apparatus and condensation of volatile components remaining in the mold apparatus. A mechanism can be installed. Usually, the thickness of the gas vent is formed to a depth of 50 to 150 nm. The gas vent may be provided in a part of the cavity, but it is also preferably formed in the entire surface except the gate portion. In addition, such a gas vent may be formed in the gate portion or the runner portion of the mold apparatus.

Although the injection molding machine used for injection molding is not specifically limited, For example, as a cylinder system, in-line system, preliminary plasticization system; As a drive system, a hydraulic, electric, hybrid type; Examples of the clamping method include direct pressure and toggle type; Examples of the injection direction include a horizontal type and a vertical type. In addition, the clamping method may be one capable of injection compression. The cylinder diameter and the clamping force are determined depending on the shape of the desired molded article, but in general, it is preferable to increase the clamping force when the projected area of the molded article is large, and to increase the cylinder diameter when the capacity of the molded article is large.

When the cylinder is an inline type, the screw shape such as compression ratio, length / diameter ratio, presence or absence of a sub-flight can be appropriately selected, and a well-known coating such as chromium, titanium, nitride, or carbon can be applied to the screw surface. . In addition, in order to improve the stability of the metering or injection operation, a mechanism for controlling the rotation of the screw or the pressure can be provided. In addition, it is preferable to reduce the pressure in the cylinder or the hopper for storing the resin composition, or to seal the cylinder and the hopper with an inert gas such as nitrogen, from the viewpoint of obtaining a stable molded article.

In injection molding, a method of reducing the pressure in the cavity of the mold apparatus or an injection compression method is preferably used in order to reduce the warpage of the molded article or to make stable continuous molding.

In the case of injection molding by reducing the inside of the cavity of the mold apparatus, the degree of reduced pressure is preferably -0.08 MPa or less, more preferably -0.09 MPa or less, particularly preferably -0.1 MPa or less. If the above range is exceeded, a molded article excellent in light transmittance and light diffusing property may not be obtained due to insufficient degree of reduced pressure.

The degree of reduced pressure in this range is achieved using known methods, for example using a vacuum pump. It is preferable to use well-known sealing materials, such as an O-ring, around a cavity, an ejector mechanism part, etc., and vacuum grease etc. can be used in the range which impurity does not mix in a molded article. In addition, although the suction port for connecting with a decompression device, such as a vacuum pump, can be provided in arbitrary places in a metal mold | die apparatus, it is normally provided in the ejector mechanism part, the end of a sprue and a runner, an overlapping structure part, etc. In addition, the vacuum suction sequence is not particularly limited as long as it can be controlled by a solenoid valve or the like in accordance with opening and closing of the mold apparatus, can be operated at all times, and can be made inside the cavity of the mold apparatus at a desired reduced pressure during filling of the molten resin.

When injection molding by depressurizing the inside of the cavity of a die apparatus, since injection of molten resin is carried out in the state which closed the cavity and reduced pressure, injection delay time is normally set. Injection delay time depends on the capacity and cavity size of the vacuum pump used, but is typically on the order of 0.5 to 3 seconds.

On the other hand, in the injection compression molding method, the cavity interval is set to 1.5 to 20 times the thickness of the molded article, the molten resin is injected into the gap, and the pressure of the resin measured at the cylinder side is maintained in the range of 200 to 2,000 kgf / cm ² , What is necessary is to compress the molded object surface in a metal mold | die apparatus, and narrow the space | interval of a cavity.

In addition, the core of the mold apparatus is set to 1.1 times to 10 times the thickness of the molded article to be in a movable state, and the molten resin is injected therein to move the core on the movable side from an average of 0.01 mm / sec to 1 mm / after injection start or injection end. Can compress in seconds.

Known molding machines are used for these injection compression molding methods.

Although other conditions of injection molding are not specifically limited, Usually, cylinder temperature is 260-350 degreeC, and mold apparatus temperature is normally Tg-1-Tg-40 degreeC based on the glass transition temperature Tg of cyclic olefin resin, Preferably Is in the range of Tg-5 to Tg-25 ° C. In addition, although the injection speed varies depending on the size of the molded article of the present invention or the cylinder size of the molding machine, for example, when the cylinder diameter is 28 mm, it is usually 80 mm / sec or more, preferably 90 to 250 mm / sec. In holding pressure, it is preferable to adjust suitably to the minimum pressure and time of the grade which can maintain the shape of a molded article.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. In the following, "parts" and "%" are "parts by weight" and "% by weight" unless otherwise specified.

<Method for Measuring Physical Properties of Cyclic Olefin-Based Resin>

In addition, the various physical properties of cyclic olefin resin were measured by the following method.

Refractive index

Cyclic olefin resin was injection molded to prepare a 40 mm x 60 mm x 3.2 mm flat plate, and annealing was performed at (Tg + 5) ° C for 30 minutes. Then, after leaving for 1 week in 25 degreeC and 50 RH% environment, the refractive index was measured using the refractive index (PR-2 by Carl Zeiss Corporation) in 25 degreeC and 50 RH% environment.

(Intrinsic viscosity: η _inh )

Using a chloroform as a solvent, a sample having a polymer concentration of 0.5 g / dl was prepared, and measured on a Ubelode viscometer under the conditions of 30 ° C.

(Molecular Weight)

Using HLC-8020 gel permeation chromatography (GPC, column: TSKgel G7000HXL × 1, TSKgel GMHXL × 2, and TSKgel G2000HXL × 1 in series) manufactured by Toso Industries, Ltd. It measured with the tetrahydrofuran (THF) solvent, and calculated | required the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polystyrene conversion. In addition, Mn shows the number average molecular weight of polystyrene conversion.

(Glass transition temperature: Tg)

Using DSC6200 manufactured by Seiko Instruments, Inc., the temperature was measured under a nitrogen stream at a temperature increase rate of 20 ° C./min.

(Melt viscosity)

Melt viscosity was measured using a twin capillary rheometer. Three measurement points were arbitrarily selected from 240 degreeC, 260 degreeC, 280 degreeC, 300 degreeC, and 320 degreeC, and melt viscosity was measured in the range of 10 to 10,000 s <^-1> shear rate in each temperature. Based on the measured data, fitting was performed by the least square method (Equation 1) to determine coefficients and constants.

<Synthesis of cyclic olefin resin>

Synthesis Example 1

250 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene as cyclic olefin, 41 parts of 1-hexene as molecular weight regulator, and for ring-opening polymerization reaction 750 parts of toluene were put into the reaction container which carried out the nitrogen substitution as a solvent, and this solution was heated at 60 degreeC. Subsequently, 0.62 parts of toluene solution (concentration 1.5 mol / L) of triethyl aluminum and tungsten chloride (t-butanol: methanol: tungsten = 0.35 mol: 0.3 mol) modified with t-butanol / methanol were added to the solution in the reaction container. 3.7 parts of: 1 mol) toluene solution (concentration 0.05 mol / L) were added, and this solution was heat-stirred by heating and stirring at 80 degreeC for 3 hours, and the solution containing a ring-opening polymer was obtained.

The polymerization conversion rate in this polymerization reaction was 97%.

4,000 parts of the ring-opening polymer solution thus obtained were put into an autoclave, 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution, and the hydrogen gas pressure was 100 kg / cm ² and the reaction temperature. The hydrogenation reaction was performed by heat-stirring for 3 hours on condition of 165 degreeC. After cooling the obtained reaction solution (solution containing a hydrogenated polymer), hydrogen gas was discharged.

This reaction solution was then poured into a large amount of methanol to coagulate and recover the hydrogenated polymer.

Thereafter, the recovered hydrogenated polymer was dissolved in toluene to prepare a solution having a concentration of 20%, filtered through a filter having a pore size of 1 µm, and then poured into a large amount of methanol to coagulate and recover the hydrogenated polymer. This redissolution / precipitation / recovery operation was repeated three times, and finally, the obtained hydrogenated polymer was dried at 100 ° C. under reduced pressure for 12 hours, and then granulated using a melt extruder to obtain pellets.

Thus, the hydrogenation rate of the obtained hydrogenated polymer (henceforth "cyclic olefin resin (1)") was measured on 400 MHz conditions by ¹ H-NMR. The hydrogenation rate was substantially 100%.

In addition, the refractive index at 28 _degreeC of cyclic olefin resin (1) was 1.51, (eta) _h was 0.52, Mw was 75,000, Mw / Mn was 3.5, and Tg was 164 degreeC.

As shown in FIG. 7, the melt viscosity was measured, and fitting was performed to calculate a constant. n = 0.462, tau ^* = 1.55 * 10 <^4> , B = 4.09 * 10 <^-10> , Tb = 16920.

Synthesis Example 2

225 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene and 25 parts of bicyclo [2.2.1] hept-2-ene as cyclic olefins A hydrogenated polymer was obtained in the same manner as in Synthesis example 1 except that 43 parts of 1-hexene was used as the molecular weight regulator. The hydrogenation rate of the obtained hydrogenated polymer (henceforth "cyclic olefin resin (2)") was substantially 100%.

The refractive index at 28 _degreeC of cyclic olefin resin (2) was 1.51, (eta) _h was 0.50, Mw was 62,000, Mw / Mn was 3.5, and Tg was 141 degreeC.

As shown in Fig. 8, the melt viscosity was measured, and fitting was performed to calculate a constant. n = 0.393, tau ^* = 7.12 * 10 <^4> , B = 6.96 * 10 <^-9> , Tb = 14030.

Synthesis Example 3

250 parts of 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene were used as cyclic olefin, and 750 parts of cyclohexane were used as a solvent for ring-opening polymerization reaction, and it is the same as that of the synthesis example 1 To obtain a hydrogenated polymer. The hydrogenation rate of the obtained hydrogenated polymer (henceforth "cyclic olefin resin (3)") was substantially 100%.

The refractive index at 28 _degreeC of cyclic olefin resin (3) was 1.52, (eta) _h was 0.50, Mw was 65,000, Mw / Mn was 3.0, and Tg was 145 degreeC.

As shown in FIG. 9, melt viscosity was measured, and fitting was performed to calculate a constant. n = 0.264, tau ^* = 2.04 * 10 <^5> , B = 6.13 * 10 <^-7> , Tb = 11160.

[Examples 1 to 8 and Comparative Examples 1 to 5]

<Production of Optical Lens Molded Body>

(Drying of cyclic olefin resin)

The cyclic olefin resin was previously vacuum dried at 100 ° C. for 4 hours, returned to normal pressure in a nitrogen atmosphere, and then sealed in a bag made of aluminum sealed with nitrogen.

(mold)

As shown in Tables 1 and 2, the mold apparatus shown in Figs. 10 and 11A to 11C was used. The cavity of these mold apparatuses has the space part corresponding to each of the flange part, the recessed part, and the lens part of an optical lens molding. In addition, in the metal mold | die apparatus used by the Example and the comparative example, FIG. 10 has shown the cavity part, and FIG. 11A-11C has shown the gate part.

In addition, a gas vent (not shown) having a depth of 100 μm was provided on the entire surface except the gate at a length of 2 mm around the cavity.

(Injection molding)

The cyclic olefin resin was injection-molded using the injection molding machine ((alpha) 2000i100B by Panak Corporation, cylinder diameter 26mm, nozzle diameter 2.5mm, and 100 tons of shapes). Molding conditions were as shown in Tables 1 and 2.

On the other hand, the screw rotation speed at the time of metering was 40 rpm, back pressure was 60 kgf / cm <^2> , and the shaping cycle was 45 seconds. Furthermore, 30 shot molding was performed after shaping | molding conditions were set, and the 10 molded articles of the lens obtained after that were used as the product.

<Evaluation method>

The molded object (optical lens molded object) obtained by the said injection molding was evaluated by the following method. The results are shown in Tables 1 and 2.

(Surface precision)

The difference in the maximum value and minimum value of the deviation from the reference surface of the obtained optical lens molded object, and Pv value were measured using the form Tallysurf S6 by Taylor Hobson. 12 and 13, measurements were made in the x direction and the y direction on the r1 plane and the r2 plane, respectively. (Circle), the case where this Pv value is less than 0.5 micrometer, and the case where (circle) and 1.0 micrometer or more are less than 1.0 micrometer and the case where (triangle | delta) and 2.0 micrometer or more were made into (circle) and 0.5 micrometer or more and less than 1.0 micrometer.

(Optical deformation)

The in-plane phase difference distribution of the obtained optical lens was measured using the CCD Cobra by the Oji Corporation. (Circle) and the case where the largest phase difference measured in an effective surface are less than 100 nm (circle) and the case where it is 100 nm or more and less than 140 nm were made into (circle), and the case where 140 nm or more and less than 160 nm were (triangle | delta) and 160 nm or more.

(Flow mark)

The lens surface was observed with the actual microscope manufactured by Olympus. (Circle) and the case where a flow mark is observed were made into the case where a flow mark is not observed.

Examples 1 to 8 are cases where the speed v _max satisfies the scope of the present invention, and Comparative Examples 1 to 5 were cases where the speed v _max did not satisfy the scope of the present invention.

From Tables 1 and 2, the optical lens molded article of Comparative Example was not balanced with optical deformation and surface precision, but the optical lens molded article of Example had a good balance of optical deformation and surface precision.

The thin optical lens compact according to the present invention is useful as an optical lens such as a camera module of a mobile phone, a camera module of a personal computer, and the like.

FIG. 1 (a) is an external view of a cavity viewed from the vertical direction in the mold apparatus preferably used in the present invention, and FIG. 1 (b) is a cross-sectional view along the line A in FIG. 1 (a).

Fig. 2 (a) is an external view of a cavity viewed from the vertical direction in the mold apparatus preferably used in the present invention, and Fig. 2 (b) is a cross-sectional view along the line A in Fig. 2 (a).

Fig. 3 (a) is an external view of the cavity viewed from the vertical direction in the mold apparatus preferably used in the present invention, and Fig. 3 (b) is a cross-sectional view along the line A in Fig. 3 (a).

4 (a) and 4 (b) are external views of a cavity viewed from the vertical direction in the mold apparatus preferably used in the present invention, and FIG. 4 (c) is a line in FIGS. 4 (a) and 4 (b). A cross section along A.

Fig. 5 is an external view of the lens section in the vertical direction in the optical lens molded article obtained in the present invention.

FIG. 6A is a cross-sectional view along the line A in FIG. 5.

FIG. 6B is a cross-sectional view along the line A in FIG. 5.

FIG. 6C is a cross-sectional view along the line A in FIG. 5.

FIG. 6D is a cross-sectional view along the line A in FIG. 5.

FIG. 6E is a cross-sectional view along the line A in FIG. 5.

FIG. 6F is a cross-sectional view along the line A in FIG. 5.

It is a figure which shows the result of having measured melt viscosity of cyclic olefin resin (1).

8 shows the results of measuring melt viscosity of cyclic olefin resin (2).

It is a figure which shows the result of having measured melt viscosity of cyclic olefin resin (3).

10 (a) is an external view of the cavity viewed from the vertical direction in the mold apparatus used in the embodiment, and FIG. 10 (b) is a cross-sectional view along the line A in FIG. 10 (a).

FIG. 11A (a) is an external view of a gate viewed from the vertical direction in the mold apparatus used in the embodiment, and FIG. 11A (b) is a cross-sectional view along the line A in FIG. 11A (a).

FIG. 11B (a) is an external view of the gate viewed in the vertical direction in the mold apparatus used in the embodiment, and FIG. 11B (b) is a cross-sectional view along the line A in FIG. 11B (a).

FIG. 11C (a) is an external view of a gate viewed in the vertical direction in the mold apparatus used in the embodiment, and FIG. 11C (b) is a cross-sectional view along the line A in FIG. 11C (a).

It is a figure for demonstrating the measuring method of surface precision.

FIG. 13 is a cross-sectional view along the line Y in FIG. 12.

Claims (2)

The molten cyclic olefin resin is injected from the nozzle of the injection molding machine, the cavity of the mold apparatus is filled with the cyclic olefin resin, A flange portion and a lens portion are joined via a concave portion, wherein the thickness of the flange portion is 0.5 mm or less, the thickness of the concave portion is 0.4 mm or less while being less than the thickness of the flange portion, and the optical lens molded body having a diameter of 10 mm or less. Way, The manufacturing method of the optical lens molded object characterized by filling so that the value _vmax at the highest speed among the speed v of the said cyclic olefin resin in the injection direction from the said nozzle may be 2500-20000 mm / s. The method for producing an optical lens molded article according to claim 1, wherein the cyclic olefin resin contains at least one polar group.

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