KR101339473B1 - Process for producing a molded optical lens of thin configuration - Google Patents

Abstract

The present invention provides a thin optical lens molded article having small optical deformation and excellent stability of surface accuracy.

According to the present invention, a cyclic olefin resin is injection molded by a mold apparatus in which a cavity corresponding to an optical lens molded body and a gate are coupled through a gate opening, and a flange portion and a lens portion are coupled through a recess, and the thickness of the flange portion is increased. Is 0.5 mm or less, the thickness of the recess is 0.4 mm or less while the thickness of the flange is less than or equal to 10 mm, and the diameter is 10 mm or less, and the thickness of the gate in the height direction of the cavity in the gate opening is measured. t ₁ and the thickness t ₂ of the flange portion in the height direction of the cavity at the gate opening satisfy the following expression (1), and the gate is narrowed toward one side of the height direction of the cavity toward the gate opening. , The mold length in which the inclination angle β narrowing in the height direction satisfies Equation 2 below. By, the present invention relates to a method for producing an optical lens molded article which comprises injection molding a cyclic olefin resin.

&Quot; (1) "

t ₂ × 0.1≤t ₁ ≤t ₂ × 0.8

&Quot; (2) "

20 ° ≤β≤60 °

Optical lens molded body, cyclic olefin resin, mold apparatus, gate

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. In more detail, this invention relates to the manufacturing method of a thin optical lens molded object which performs injection molding using the metal mold | die apparatus which has a specific gate.

2. Description of the Related Art In recent years, the thickness of a camera lens module mounted on a mobile phone has been reduced due to the thinness of the main body of the mobile phone. In the thinning of the camera lens module, the thickness of the optical lens, which is a component constituting the module, is designed to be thin.

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] JP-A-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, and surface precision falls.

Accordingly, an object of the present invention is to provide a method for producing a thin optical lens molded body having small optical deformation and excellent stability of surface accuracy.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, when the injection molding is carried out using the metal mold | die apparatus which has a specific gate, it discovered that the optical lens molded object which was small in optical deformation and excellent in stability of surface precision can be manufactured. Thus, the present invention has been completed.

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

Injection molding the cyclic olefin resin by a mold apparatus in which a cavity and a gate corresponding to the optical lens molded body are coupled through the gate opening,

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 thickness t ₁ of the gate in the height direction of the cavity at the gate opening and the thickness t ₂ of the flange portion in the height direction of the cavity at the gate opening satisfy the following expression (1), and the gate is the gate One side of the height direction of the said cavity becomes narrow toward an opening part, and the said cyclic olefin resin is injection-molded by the said mold apparatus which the inclination-angle (beta) narrowing in the said height direction satisfy | fills following formula (2). do.

t ₂ × 0.1≤t ₁ ≤t ₂ × 0.8

20 ° ≤β≤60 °

It is preferable that both sides of the width direction of the cavity are narrowed equally toward the gate opening, and the inclination angle α narrowing in the width direction satisfies the following expression (3).

30 ° ≤α≤60 °

Alternatively, it is preferable that both sides of the width direction of the cavity are equally widened toward the gate opening, and the inclination angle α widening in the width direction satisfies the following expression (4).

30 ° ≤α≤60 °

The gate has a flat portion and is coupled to the cavity via the flat portion, and the length L of the flat portion is preferably 0.2 to 2.0 mm.

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.

Hereinafter, the present invention will be described in detail.

The manufacturing method of the optical lens molded object which concerns on this invention is a method of injection-molding cyclic olefin resin by the metal mold | die apparatus which has a specific gate, and manufactures the optical lens molded object which has a specific shape.

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 polymerizing a monomer containing the 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 monovalent polar group. In this case, as the hydrocarbon group represented by R ¹ or R ³ , an alkyl group is preferable, and a methyl group is particularly 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, the hydrocarbon group is preferably an alkyl group. Further, n is usually from 0 to 5, and a cyclic olefin having a smaller value of n is preferable because a cyclic olefin resin having a higher glass transition temperature can be obtained, and a cyclic olefin (-COOR) in which n is 0 can be easily synthesized 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 an integer of 0 to 3; p represents 0 or a positive integer, Preferably it represents the integer of 0-3. More preferably, m + p is an integer of 0 to 4, particularly preferably m + p is an integer of 0 to 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 singly or in combination of two or more kinds.

Specific examples of the cyclic olefin include, but are not limited to, the following 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 .0 ^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,

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-ethylidenbicyclo [2.2.1] hept-2-ene,

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

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

8-phenyltetracyclo [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-

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

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

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-

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

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

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,

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

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-heptafluoropropoxytetracyclo [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 ]

8,9-difluoro-8-heptafluoroisopropyl-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,

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

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

As the (co) polymer obtained by polymerizing the monomer containing the cyclic olefin compound, specifically,

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

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

(3) a hydrogenated (co) polymer of the ring-opened (co) polymer of (1) or (2)

(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 and an unsaturated double bond-containing compound represented by the above formula (1)

(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) a ring-opening polymer and (2) a ring-

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.

&Lt; Copolymerizable monomers &

The copolymerizable monomers include cycloolefins, and cycloolefins having preferably 4 to 20 carbon atoms, and more preferably 5 to 12 carbon atoms are preferable. More specifically, examples include cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. These cycloolefins may be used singly or in combination of two or more kinds.

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 a case where the cyclic olefin is homopolymerized.

<Catalyst for ring opening polymerization>

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

(a) at least one compound selected from the group consisting 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 above-mentioned metathesis catalyst may contain 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 solution of the molecular weight modifier described later, or as a solvent for the cyclic olefin and / or metathesis catalyst. Examples of such a solvent include alkanes such as pentane, hexane, heptane, octane, nonane and decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; Halogenated alkanes such as chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chloroform and tetrachlorethylene; Halogenated aryl such as chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate and methyl propionate; And ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These solvents may 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.

&Lt; Molecular weight regulator &

The molecular weight of the resulting ring-opened (co) polymer can be controlled by the polymerization temperature, the type of catalyst and the type of solvent, but can also be controlled by coexistence of a molecular weight regulator.

Preferable examples of the molecular weight regulator include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, Among them, 1-butene and 1-hexene are particularly preferable. These molecular weight modifiers can be used alone or in combination of two or more.

The amount of the molecular weight modifier to be used is generally 0.005 to 0.6 mol, preferably 0.01 to 0.5 mol, per 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, an 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) polymer

The ring-opened (co) polymer can be used as it is, but the hydrogenated (co) polymer (3) obtained by further hydrogenation is useful as a resin having excellent 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.

<Hydrogenation catalyst>

As the hydrogenation catalyst, a catalyst used for the hydrogenation reaction of a typical olefinic compound can be used. Examples of the hydrogenation catalyst include heterogeneous catalysts and homogeneous catalysts.

Examples of the heterogeneous catalyst include solid catalysts in which noble metal catalyst materials such as palladium, platinum, nickel, rhodium, and ruthenium are supported on a carrier such as carbon, silica, alumina, or titania. 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 hydrogenation catalysts are preferably used in such a ratio that the weight ratio of ring-opening (co) polymer and hydrogenation catalyst (ring-opening (co) polymer: 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. The higher the hydrogenation rate, the more excellent the stability against heat and light, and the molded article such as a light guide having stable characteristics over a long period of time can be obtained.

The content of the gel in the hydrogenated (co) polymer (3) is preferably 5% by weight or less, more preferably 1% by weight or less.

(4) Hydrogenated (co) polymer

The hydrogenated (co) polymer (4) is obtained by cyclizing the ring-opened (co) polymer of (1) or (2) by the Friedel-Crafts reaction and then hydrogenating.

A method of cyclizing the ring-opened (co) polymer by a Friedel-Crafts reaction is not particularly limited, and a known method using an acidic compound described in Japanese Patent Application Laid-Open (kokai) No. 50-154399 can be employed .

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-opened (co) polymer may be hydrogenated in the same manner as the hydrogenation reaction of (3).

(5) Saturated copolymer

The saturated copolymer (5) is obtained by subjecting the cyclic olefin to addition polymerization of an unsaturated double bond-containing compound in the presence of an addition polymerization catalyst. As the addition polymerization method, conventionally known methods can be applied.

<Unsaturated double bond-containing compound>

Examples of the unsaturated double bond-containing compound include olefinic compounds such as ethylene, propylene, and butene. Of these, olefinic compounds preferably having 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms are preferable Do.

The amount of the unsaturated double bond-containing compound to be used is preferably 90/10 to 40/60, more preferably 85/15 to 50/50, in terms of the weight ratio of the cyclic olefin to the unsaturated double bond-containing compound (cyclic olefin / unsaturated double bond- Is more preferable. Provided that the total weight of the cyclic olefin and the unsaturated double bond-containing compound is 100.

<Addition polymerization catalyst>

Examples of the addition polymerization catalyst include a combination of at least one compound selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a cocatalyst.

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 organoaluminum compound may be used alone, or two or more of them may be used in combination.

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.

Examples of the solvent used in the addition polymerization reaction include the solvents exemplified in the above ring-opening (co) polymerization reaction.

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.

&Lt; Vinyl cyclic hydrocarbon monomer >

Examples of the vinyl cyclic hydrocarbon-based monomer include vinyl cyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene; Vinylated 5-membered cyclic hydrocarbon monomers such as vinyl cyclopentane-based monomers such as 4-vinyl cyclopentane and 4-isopropenyl cyclopentane; Vinyls such as 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene and 2-methyl- Cyclohexene-based monomers; Vinylcyclohexane-based monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane; Styrene monomers such as styrene,? -Methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene and 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; Vinyl cycloheptane-based monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane, and the like. Among these monomers, styrene and? -Methylstyrene are preferable. These monomers may be used singly or in combination of two or more kinds.

&Lt; Cyclopentadiene-based monomer >

As said cyclopentadiene type monomer, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopenta Dienes and the like. Among these monomers, cyclopentadiene is preferred. These monomers may be used singly or in combination of two or more kinds.

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

The hydrogenated (co) polymer of the addition type (co) polymer (6) can be obtained by hydrogenating the addition type (co) polymer (6) in the same manner as in the above (3).

(7) Alternating copolymer

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

<Acrylate>

Examples of the acrylate include linear, branched or cyclic alkyl acrylates having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate; Acrylate containing a heterocyclic group having 2 to 20 carbon atoms such as glycidyl acrylate and 2-tetrahydrofurfuryl acrylate; Aromatic group-containing acrylates having 6 to 20 carbon atoms such as benzyl acrylate; Acrylate having a polycyclic structure having 7 to 30 carbon atoms such as isobornyl 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 the Lewis acid to be used is preferably 0.001 to 1 mole based on 100 moles of the acrylate.

In addition, known organic peroxides or azobis-based radical polymerization initiators which generate free radicals may be used.

The polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. Examples of the solvent for the polymerization reaction include the solvents exemplified in the ring-opening (co) polymerization reaction.

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, the acrylate-derived structural units 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. Further, using tetrahydrofuran as a solvent, measurement was conducted by gel permeation chromatography (GPC, column: TSKgel G7000HXL x 1, TSKgel GMHXL x 2 and TSKgel G2000HXL x 1, four in series connected) The molecular weight in terms of polystyrene is preferably from 8,000 to 100,000, more preferably from 10,000 to 80,000, particularly preferably from 12,000 to 50,000, and the weight average molecular weight (Mw) is preferably from 20,000 to 300,000, More preferably from 30,000 to 250,000, and particularly preferably from 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.

The glass transition temperature (Tg) of the cyclic olefin based resin is usually 120 占 폚 or higher, preferably 120 to 350 占 폚, more preferably 120 to 250 占 폚, particularly preferably 130 to 200 占 폚. The cyclic olefin-based resin having a Tg within the above range is hard to be deformed even in use under high temperature conditions or in secondary processing accompanied by heating such as coating and printing, and also has excellent molding processability, It is difficult to occur.

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 (5).

On the other hand, thermoplastic resins are generally non-Newtonian fluids whose apparent viscosity changes with shear rate. Several rheological models have been proposed to describe the viscosity characteristics of these non-Newtonian fluids, but a modified cross model defined by Equation 5 below is used.

The cyclic olefin-based resin used in the present invention is characterized in that the change of the melt viscosity to a certain degree is greater than the shear rate. This characteristic is expressed by the value of the exponent constant n in the above expression (5), and the larger the value of n, the larger the change in the melt viscosity with respect to the shear rate.

The cyclic olefin resin used in the present invention has an n of 0.3 or more and 0.5 or less. When n is less than 0.3, fluidity at the thin portion 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 in the thick portion at the lens portion and at the same time, 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, in the production of a thin optical lens having the above-described shape, a cyclic olefin resin having n in the above range is preferably used.

The cyclic olefin resin used in the present invention is preferably subjected to removal of dissolved water or oxygen components by a method known in advance 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 vacuum dryer or a dryer that circulates an inert gas such as nitrogen from the viewpoint of easily obtaining a molded article having color uniformity.

The drying temperature and the drying time are not particularly limited, but they are usually dried at Tg-100 ° C to Tg-20 ° C for 2 to 6 hours.

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 have a diameter of 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 less than 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 portion means a value measured at the position of the lens end portion. 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 in the direction of the lens portion. And the concave portion means a value measured at a position where the thickness of the thin portion 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 reducing the thickness of the camera device mounted on a portable telephone or the like.

3. Mold device

In the present invention, in the mold apparatus used for injection molding the cyclic olefin resin, the cavity and the gate are coupled through the gate opening as shown in FIG. The cavity has a shape corresponding to the optical lens molded body, and has a flange portion, a recess, and a space corresponding to each of the lens units 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 used in the present invention, the thickness t ₁ of the gate in the height direction of the cavity in the gate opening and the flange portion in the height direction of the cavity in the gate opening are shown. The thickness t ₂ of satisfies Equation 1 below, and the gate is narrowed toward one side in the height direction of the cavity toward the gate opening, and the inclination angle β narrowing in the height direction satisfies Equation 2 below. It is characterized by.

&Quot; (1) &quot;

t ₂ × 0.1≤t ₁ ≤t ₂ × 0.8

&Quot; (2) &quot;

20 ° ≤β≤60 °

If t ₁ is smaller than t ₂ × 0.1, the surface precision of the optical lens molded body may be inferior, and if t ₁ is larger than t ₂ × 0.8, local optical deformation is likely to occur in the optical lens molded body. In addition, when β is smaller than 20 °, local optical deformation is likely to 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.

As shown in FIG. 2, it is preferable that both sides of the cavity in the width direction are equally narrowed toward the gate opening, and the inclination angle α narrowing in the width direction satisfies the following expression (3).

&Quot; (3) &quot;

30 ° ≤α≤60 °

Or as shown in FIG. 3, it is preferable that both sides of the width direction of the said cavity become equally wide toward the said gate opening part, and the inclination-angle (alpha) extended in the said width direction satisfy | fills following formula (4). Do.

&Quot; (4) &quot;

30 ° ≤α≤60 °

In any of the above equations (3) and (4), when α is smaller than 30 °, local optical deformation may occur in the optical lens molded body, and when α is larger than 60 °, the surface precision of the optical lens molded body is deteriorated, Flow marks may occur.

In addition, it is preferable that the gate has a flat portion as shown in FIG. 4, and is coupled to the cavity through the flat portion, and the length L of the flat portion is 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.

On the other hand, the molded article (optical lens molded article) obtained by the present invention has the shape as described above and is manufactured using a mold apparatus having a known material. Preferred materials for the mold apparatus include ordinary carbon steel, stainless steel, or known alloys based on these, and the surface of the mold apparatus may be quenched, known coating treatment with chromium, titanium, diamond, or the like, 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 can be formed in the gate portion or the runner portion of the mold apparatus.

4. Injection molding

In this invention, the said cyclic olefin resin is injection-molded by the metal mold | die apparatus which has the said gate, and the optical lens molded object which has the said shape is manufactured.

The injection molding machine used for injection molding is not particularly limited as long as the above-mentioned mold apparatus can be used. Examples of the injection molding machine include, for example, an in-line method and a preliminary plasticization method; Driving methods include hydraulic, electric, hybrid; Examples of clamping methods 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 injection compression. The cylinder diameter and the clamping force are determined by the shape of the desired molded part, but in general, when the projected area of the molded part is large, it is preferable to increase the clamping force, and when the capacity of the molded part is large, the cylinder diameter is preferably increased. Do.

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. . Further, in order to improve the stability of the metering or injection operation, a mechanism for controlling rotation and pressure of the screw may be provided. In addition, it is preferable to reduce the pressure inside 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, because the molded article can be stably obtained.

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. When the amount exceeds the above range, a reduced pressure degree is insufficient and a molded article excellent in light transmittance and light diffusibility may not be obtained.

The reduced pressure in the above range is achieved by using a known method, for example, a vacuum pump. It is preferable to use a known sealing material such as an O-ring or the like around the cavity or the ejector mechanism portion, and vacuum grease or the like can be used within such a range that impurities are not mixed in the 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 the opening and closing of the mold apparatus, can be operated at all times, and the inside of the cavity of the mold apparatus can be 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.

A known molding machine is 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. 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, the injection speed is usually 80 mm / second or more, preferably 90 to 250 mm / second. 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, the present invention will be described by way of examples, but the present invention is not limited by these examples. 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>

Various physical properties of the cyclic olefin resin were measured by the following methods.

Refractive index

A cycloolefin resin was injection molded to prepare a flat plate of 40 mm x 60 mm x 3.2 mm and annealed at (Tg + 5) DEG C for 30 minutes. Thereafter, the sample was further left for one week under an environment of 25 ° C and 50 RH%, and then the refractive index was measured using a refractive index meter (PR-2 manufactured by Kesztyn example) under the environment of 25 ° C and 50 RH%.

(Intrinsic viscosity _{:? Inh} )

A sample having a polymer concentration of 0.5 g / dl was prepared using chloroform as a solvent and measured with a Ubbeloid viscometer under the condition of 30 캜.

(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. On the other hand, Mn represents the number average molecular weight in terms of polystyrene.

(Glass transition temperature: Tg)

DSC6200 manufactured by Seiko Instruments Inc. under a nitrogen gas stream at a heating rate of 20 DEG C / min.

(Melt viscosity)

Melt viscosity was measured using a twin capacitive rheometer. Three points were arbitrarily selected from 240 ° C, 260 ° C, 280 ° C, 300 ° C and 320 ° C, and the melt viscosity was measured at a shear rate of 10 to 10,000 s ^-1 at each temperature. Based on the measured data, fitting was performed by the least square method (Equation 5) to determine coefficients and constants.

&Lt; 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 a cyclic olefin, 41 parts of 1-hexene as a molecular weight regulator, 750 parts of toluene as a solvent was placed in a reaction vessel purged with nitrogen, and the solution was heated to 60 캜. Then, 0.62 part of a toluene solution of triethyl aluminum (concentration: 1.5 mol / L) and 0.62 part of tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten = : 1 mole) in toluene (concentration: 0.05 mol / L) was added to the solution, and the solution was subjected to ring-opening polymerization reaction by heating and stirring at 80 DEG C for 3 hours to obtain a solution containing a ring opening polymer.

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

In this way, into a ring-opening polymer solution was 4,000 parts obtained in the autoclave, the ring-opening RuHCl the polymer solution _{(CO) [P (C 6} H 5) 3] 3 0.48 part was added, and hydrogen gas pressure of 100 kg / cm ^2, the reaction temperature And the mixture was heated and stirred under a condition of 165 캜 for 3 hours to carry out a hydrogenation reaction. After the obtained reaction solution (solution containing hydrogenated polymer) was cooled, the hydrogen gas was purged.

Subsequently, this reaction solution was poured into a large amount of methanol to solidify the hydrogenated polymer, and recovered.

Thereafter, the hydrogenated polymer thus recovered was dissolved in toluene to prepare a solution having a concentration of 20%, filtered with a filter having a pore size of 1 탆, 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. for 12 hours under reduced pressure, 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,? ^* = 1.55 × 10 ⁴ , B = 4.09 × 10 ^-10 , and Tb = 16920.

[Synthesis Example 2]

225 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene as cyclic olefin and 25 parts of bicyclo [2.2.1] hept- , And 43 parts of 1-hexene as a molecular weight regulator was used. The hydrogenation rate of the resulting hydrogenated polymer (hereinafter referred to as "cycloolefin resin (2)") was substantially 100%.

The cycloolefin resin (2) had a refractive index of 1.51 at 28 占 폚,? _Inh of 0.50, Mw of 62,000, Mw / Mn of 3.5, and Tg of 141 占 폚.

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

[Synthesis Example 3]

Except that 250 parts of 8-ethylidene tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene was used as the cyclic olefin and 750 parts of cyclohexane was used as the solvent for the ring-opening polymerization reaction. To obtain a hydrogenated polymer. The hydrogenation rate of the resulting hydrogenated polymer (hereinafter referred to as "cycloolefin resin (3)") was substantially 100%.

The cycloolefin resin (3) had a refractive index of 1.52 at 28 占 폚,? _Inh of 0.50, Mw of 65,000, Mw / Mn of 3.0, and Tg of 145 占 폚.

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

[Examples 1 to 10 and Comparative Examples 1 to 5]

<Production of Optical Lens Molded Body>

(Drying of cyclic olefin resin)

The cyclic olefin resin was vacuum-dried at 100 占 폚 for 4 hours in advance, returned to normal pressure in a nitrogen atmosphere, and sealed in an aluminum bag sealed with nitrogen.

(mold)

As shown in Tables 1 and 2 below, the mold apparatuses shown in FIGS. 10A to 10B and 11A to 11I were used. The cavity of these mold apparatuses has a space part corresponding to each of a flange part, a recessed part, and a lens part of an optical lens molding. On the other hand, in the mold apparatus used by the Example and the comparative example, FIGS. 10A-10B have shown the cavity part, and FIGS. 11A-11I have 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) 2000iB by a panax company, cylinder diameter 25mm, clamping 100 ton). Molding conditions were as shown in Tables 1 to 3 below.

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. Moreover, 30 shot shaping | molding was performed after shaping | molding conditions were set, and 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 3.

(Cotton 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 strain)

The in-plane phase difference distribution of the obtained optical lens molded object 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 1-10 are the case where injection molding was carried out by the metal mold | die apparatus provided with the shape mentioned above, and Comparative Examples 1-5 were the case where injection molding was carried out by the metal mold | die apparatus which does not have the shape mentioned above.

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 molded article 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, or the like.

FIG. 1 (a) is an external view of a cavity viewed from the vertical direction in the mold apparatus 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 used in the present invention.

Fig. 3 (a) is an external view of the mold apparatus used in the present invention as seen from the vertical direction.

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

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).

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

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

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

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

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

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

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

FIG. 11I (a) is an external view of the gate viewed from the vertical direction in the mold apparatus used in the embodiment, and FIG. 11I (b) is a cross-sectional view along the line A in FIG. 11I (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 (5)

Injection molding the cyclic olefin resin by a mold apparatus in which a cavity and a gate corresponding to the optical lens molded body are coupled through the gate opening, 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 thickness t ₁ of the gate in the height direction of the cavity at the gate opening and the thickness t ₂ of the flange portion in the height direction of the cavity at the gate opening satisfy the following expression (1), and the gate is the gate One side of the height direction of the said cavity becomes narrow toward an opening part, and the said cyclic olefin resin is injection-molded by the said mold apparatus which the inclination-angle (beta) narrowing in the said height direction satisfy | fills following formula (2). The manufacturing method of the optical lens molded object made. &Quot; (1) &quot; t ₂ × 0.1≤t ₁ ≤t ₂ × 0.8 &Quot; (2) &quot; 20 ° ≤β≤60 ° 2. The optical as claimed in claim 1, wherein both sides of the cavity in the width direction of the cavity are equally narrowed toward the gate opening, and an inclination angle α narrowing in the width direction satisfies Equation 3 below. 3. Method for producing a lens molded body. &Quot; (3) &quot; 30 ° ≤α≤60 ° 2. The optical as claimed in claim 1, wherein both sides of the cavity in the width direction of the cavity are equally wider toward the gate opening, and an inclination angle α widening in the width direction satisfies Equation 4 below. Method for producing a lens molded body. &Quot; (4) &quot; 30 ° ≤α≤60 ° The optical lens molded product according to any one of claims 1 to 3, wherein the gate has a flat portion, is coupled to the cavity through the flat portion, and the length L of the flat portion is 0.2 to 2.0 mm. Method of preparation. The method for producing an optical lens molded article according to claim 4, wherein the cyclic olefin resin contains at least one polar group.

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