WO2007119512A1

WO2007119512A1 - Optical element and resin lens for optics

Info

Publication number: WO2007119512A1
Application number: PCT/JP2007/056175
Authority: WO
Inventors: Akiko Hara
Original assignee: Konica Minolta Opto, Inc.
Priority date: 2006-04-05
Filing date: 2007-03-26
Publication date: 2007-10-25
Also published as: JPWO2007119512A1

Abstract

Provided is an optical element wherein cracks due to moisture absorption are prevented and coloring due to thermal decomposition is eliminated when being formed, with improved hardness and a small refractive index change due to temperature. The optical element is formed by using a thermoplastic resin material wherein inorganic fine particles having an average particle diameter of 1.0-30nm are dispersed in a thermoplastic resin having a water absorption coefficient of 0.05 mass % or less.

Description

Optical element and optical resin lens

Technical field

The present invention relates to a small optical element used for an optical pickup lens or the like of an optical pickup device.

Background art

[0002] In recent years, large optical elements used as telescope lenses, microscope lenses, etc., even small optical elements used as optical pickup lenses such as CDs (Compact Discs) and DVDs (Digital Video Discs). Various plastic optical elements are manufactured and sold. These optical elements are usually manufactured through a so-called “injection molding” process in which a specific resin corresponding to the application is injected into a predetermined mold.

[0003] In general, optical elements should have low water absorption. This is because a resin having high water absorption absorbs water under high humidity, and its optical properties such as refractive index change.

[0004] When an optical element made of a hydrophobic resin is placed under high humidity, the present inventor generates moisture absorption cracks when high-temperature high-humidity is suddenly returned to room temperature, although it is not seen with water-absorbent resin. I found the problem. The hygroscopic crack referred to here is a problem in which an infinite number of cracks of about 75 m inside the optical element are visible, sparkling with the naked eye, affecting the optical properties, and reducing transparency.

[0005] The mechanism of moisture absorption cracks is that water vapor enters the gap between the resin and the resin under high temperature and high humidity. If it is returned to room temperature all at once, in the case of a water-absorbing resin, water vapor diffuses and moves in all directions in the resin and evaporates, but in the case of a hydrophobic resin, it can diffuse into the resin. Water vapor that has lost its place of agglomeration aggregates at a stretch in the gap. With this force, it is thought that the gap widens and cracks occur in the grease.

[0006] In order to prevent this crack, at present, there is also an optical element in which a hydrophilic compound (organic substance) is added (see, for example, Patent Document 1). However, although it can prevent cracks, it is an organic substance, so that a new problem of thermal decomposition and coloring during molding occurs.

Patent Document 1: JP 2002-105131 A Disclosure of the invention

Problems to be solved by the invention

An object of the present invention is to provide an optical element that prevents moisture absorption cracks, has no coloring due to thermal decomposition during molding, has improved hardness, and has a small change in refractive index with respect to temperature. Means for solving the problem

[0008] The above object of the present invention can be achieved by the following configurations.

[0009] 1. Molded using a thermoplastic resin material in which inorganic fine particles having an average particle diameter of 1.0 to 30 nm are dispersed in a thermoplastic resin having a water absorption rate of 0.05% by mass or less. An optical element characterized by the above.

[0010] 2. The optical element as described in 1 above, wherein the thermoplastic plastic resin has a polymer force represented by the following general formula (1).

[0011] [Chemical 1]

[0012] (wherein x and y are copolymerization ratios and are real numbers satisfying 50Z50 y / x≤95 / 5, n is the number of substituents Q, and an integer 0≤n≤2 R ¹ is one kind selected from a hydrocarbon group group having 2 to 20 carbon atoms, and two or more 2 + n-valent groups, and R ² is a hydrogen atom and carbon 1 or 2 or more types of monovalent groups selected, and R ³ is a hydrocarbon group group force of 2 to 10 carbon atoms. Q is COOR ⁴ (R ⁴ consists of a hydrogen atom and carbon 'hydrogen, and a structural group strength of 1 to 10 carbon atoms is also selected. 1 to 2 or more types of monovalent groups 1 type or 2 or more types of divalent groups selected from the structural group represented by

3. The optical element as described in 1 or 2 above, wherein the inorganic fine particles are acid fine particles or acid hyaluminum fine particles.

4. The optical element according to any one of 1 to 3, wherein the inorganic fine particles are subjected to a surface hydrophobization treatment. Replacement paper (MMiJ26) [0014] 5. An optical resin lens comprising the optical element according to any one of 1 to 4 above.

The invention's effect

[0015] According to the present invention, it is possible to provide an optical element that has improved hardness that prevents moisture absorption cracks, is free from coloring due to thermal decomposition during molding, and has a small change in refractive index with respect to temperature.

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] The present invention will be described in more detail.

[0017] << Inorganic fine particles >>

The inorganic fine particles used in the present invention include those that are optically transparent (having optical transparency), such as oxide fine particles, sulfide fine particles, selenium fine particles, telluride fine particles, and the like. More specifically, examples thereof include silicon oxide fine particles, acid aluminum fine particles, aluminum phosphate fine particles, titanium oxide fine particles, zinc oxide fine particles, and zinc sulfide fine particles, but are not limited thereto. Absent. Preferred are fine oxide silicon particles and fine aluminum oxide particles.

[0018] As these fine particles, one kind of inorganic fine particles may be used, or a plurality of kinds of inorganic fine particles may be used in combination.

[0019] The shape of the inorganic fine particles used in the present invention may be spherical, elliptical, flat, rod-shaped, such as V, misalignment, and the like. It can be expressed effectively. Further, the particle size distribution is not particularly limited, but in order to achieve the effect of the present invention more efficiently, a particle having a relatively narrow distribution is preferable to one having a wide distribution. Used for.

[0020] The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used. For example, methods such as thermal decomposition of metal salts and hydrolysis of metal salts and metal alkoxides are well known. As thermal decomposition of metal salts

It is obtained by spraying a metal salt or a solution thereof and thermally decomposing. For hydrolysis of metal salts and metal alkoxides, a metal salt or metal alkoxide solution is prepared in advance.

By adding water to this solution, it can be obtained by advancing hydrolysis polymerization.

[0021] The inorganic fine particles used in the present invention are inorganic fine particles having an average particle size of 1.0 to 30 nm. It is. The average particle diameter is preferably 1 nm or more and 20 nm or less, more preferably 1 nm or more and lOnm or less. If the average particle size is less than 1 nm, it is difficult to disperse the inorganic fine particles, so that desired performance may not be obtained. If the average particle size exceeds 30 nm, the resulting thermoplastic material composition may become cloudy. As a result, the transparency may be reduced and the light transmittance may be less than 70%. The average particle diameter is the diameter when the volume of inorganic fine particles is converted to a sphere. For the number of measured particles, select 100 or more particles in an electron micrograph of inorganic fine particles indiscriminately, and use the arithmetic average of the particle sizes of the individual inorganic fine particles as the average particle size.

[0022] The content of the inorganic fine particles in the plastic resin is preferably 1 to 50% by volume, more preferably 10 to 30% by volume based on the resin.

[0023] The inorganic fine particles according to the present invention preferably have a surface treated on the surface thereof.

The surface treatment method is not particularly limited, and any known method can be used.

[0024] Examples of the surface treatment agent used for the surface treatment of the inorganic fine particles include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetraphenoxysilane, methinotritrimethoxysilane, etyltrimethoxysilane, and propyltrimethoxy. Silane, Methyltriethoxysilane, Methyltriphenoxysilane, Ethyltriethoxysilane, Phenyltrimethoxysilane, 3-Methylphenyltrimethoxysilane, Dimethyldimethoxysilane, Jetyljetoxysilane, Diphenyldimethoxysilane , Diphenyldiphenoxysilane, trimethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylphenoxysilane, cyclopentyltrimethoxylane, cyclohexyltriethoxy Silane, Benjirujime chill silane, O click triethoxysilane, vinyl tri § Seto silane, Biniruto Rikuroroshiran, vinyltriethoxysilane, _I - black port trimethoxysilane, _Y - click Rollo prop Honoré methylate Honoré dichlorosilane, y Black Oral propinoremethinoresinoxysilane, γ-chloropropylmethyl _ethoxysilane , _{Ί —aminopropyltriethoxysilane} , _Ν— (j8—aminoethyl) _{Ύ —aminopropyltrimethoxysilane, Ν—} (j8— Aminoethyl) Aminopropylmethyldimethoxysilane, γ mercaptopropyltrimethoxysilane, γ—

Γ-Glycidoxypropinoremethinoresimethoxymethoxysilane, γ-methacryloxypropyltrimeth Xysilane, γ-methacryloxypropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, _Ύ — _{isocyanatopropyltriethoxysilane} , _Ί — (2-aminoethyl) aminopropylmethyldimethoxysilane , Y-linopropyltrimethyoxysilane, butyltrimethoxysilane, N-β- (Ν bulbenylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride and aminosilane compound, etc. In place of silane, aluminum, titanium, zirconia, or the like can be used, and in this case, for example, aluminum triethoxide, aluminum triisoproxide, or the like.

[0025] Also, isostearic acid, stearic acid, cyclopropanecarboxylic acid, cyclohexane carboxylic acid, cyclopentanecarboxylic acid, cyclohexanepropionic acid, octylic acid, palmitic acid, behenic acid, undecylenic acid, oleic acid, Any surface treatment agents such as fatty acids such as hexahydrophthalic acid and their metal salts, and organophosphate surface treatment agents can be used, and these should be used alone or in combination of two or more. Can do.

[0026] These compounds have different characteristics such as reaction rate, and compounds suitable for surface treatment conditions can be used. Further, only one type may be used or a plurality of types may be used in combination. Furthermore, the properties of the surface-treated fine particles obtained may vary depending on the compound used, and the affinity with the thermoplastic plastic resin used to obtain the material composition is selected by selecting the compound used for the surface treatment. It is also possible. The proportion of the surface treatment is not particularly limited, but the proportion of the surface treatment agent is preferably 10 to 99 mass% with respect to the inorganic fine particles after the surface treatment, and is 30 to 98 mass%. It is more preferable.

[0027] << Thermoplastic plastics >>

The general formula (1) of the present invention will be described.

[0028] In the general formula (1), R ¹ is preferably one or more divalent groups of which the hydrocarbon group group power having 2 to 12 carbon atoms is also selected, and more preferably This is a divalent group represented by the general formula (2).

[0029] [Chemical 2]

[0030] In the formula, p is an integer of 0 to 2.

[0031] Most preferably, it is a divalent group in which p is 0 or 1 in the general formula (2). The R ¹ structure may be used alone or in combination of two or more.

In the general formula (1), examples of R ² include hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, etc. Preferred is hydrogen and / or 1 CH, and most preferred is hydrogen.

Three

As an example of R ³ , as a preferred example of a structural unit containing this group, when _η = ο, for example, the following general formula (a), (b) or (c) can be mentioned.

[0034] [Chemical 3]

[0035] In the formula, R 'is as described above. Most preferably, it is general formula (a).

[0036] In the general formula (1), n is preferably 0.

[0037] In addition, the type of copolymerization is not limited at all in the present invention, and it is possible to apply various known copolymerization types such as random copolymer, block copolymer, alternating copolymerization, etc. A copolymer.

[0038] Further, the thermoplastic plastic resin used in the present invention is different from the paper imm) according to the molding method of the present invention. As long as it does not impair the good physical properties of the resulting product, it may have repeating structural units derived from other copolymerizable monomers as required! /, Or even! / ヽ. The copolymerization ratio is not limited, but is preferably 20 mol% or less, more preferably 10 mol% or less. If the copolymerization is further carried out, there is a possibility that optical properties will be impaired and high-precision optical components may not be obtained. is there. The type of copolymerization is not limited, but a random copolymer is preferred.

[0039] The molecular weight of the polymer represented by the general formula (1) according to the present invention is a polystyrene (or polyisoprene) converted weight measured by gel permeation chromatography (hereinafter referred to as GPC). Average molecular weight (Mw), 1,000 to 1,000,000, preferred <is 5,000 to 500, 00, more preferred <is 10,000 to 300,000, most preferred <is 50, The range is from 000 to 250,000. If the weight average molecular weight (Mw) of the polymer is excessively small, the strength characteristics of the molded product are inferior. Conversely, if the polymer is excessively large, the birefringence of the molded product increases.

[0040] The molecular weight distribution of the polymer represented by the general formula (1) according to the present invention is a force that can be appropriately selected according to the purpose of use. The weight average molecular weight in terms of polystyrene (or polyisoprene) measured by GPC The ratio (MwZMn) of (Mw) to number average molecular weight (Mn) is usually 2.5 or less, preferably 2.3 or less, more preferably 2 or less. MwZMn force Within this range, mechanical strength and heat resistance are highly balanced.

[0041] The glass transition temperature (Tg) of the polymer represented by the general formula (1) according to the present invention may be appropriately selected depending on the purpose of use, but is usually 50 ° C to 250 ° C, preferably Is 70 ° C to 200 ° C, more preferably 90 ° C to 180 ° C.

[0042] Next, the method for producing the polymer represented by the general formula (1) according to the present invention will be described.

[0043] The method for producing the polymer represented by the general formula (1) according to the present invention includes: (Method 1) copolymerizing an aromatic vinyl compound and another monomer copolymerizable with the main chain. And a method of hydrogenating carbon and aromatic bonds of aromatic rings, (Method 2) a method of copolymerizing an alicyclic vinyl compound and other monomers copolymerizable, and hydrogenating as necessary. Can be mentioned.

[0044] When the polymer represented by the general formula (1) according to the present invention is produced by the above-described method, other copolymerizable with the aromatic vinyl compound or the alicyclic vinyl compound () of Copolymer with monomer (b '), repeating unit force derived from compound (a') in copolymer D = (repeated unit chain derived from aromatic vinyl compound and Z or alicyclic vinyl compound) Weight average molecular weight), E = (weight average molecular weight of hydrocarbon copolymer (Mw) X (number of repeating units derived from aromatic vinyl compound and Z or alicyclic vinyl compound) Z hydrocarbon copolymer A copolymer having a chain structure of not more than 30%, preferably not more than 20%, more preferably not more than 15%, most preferably not more than 10% of the D force. The carbon chain unsaturated bond of an unsaturated ring such as a main chain and an aromatic ring or a cycloalkene ring can be efficiently obtained by a hydrogenation method. When D is outside the conditions specified above, the resulting polymer represented by the general formula (1) has poor low birefringence.

[0045] In the present invention, among the above production methods, the method described in (Method 1) is preferable in that the polymer represented by the general formula (1) can be obtained more efficiently.

[0046] The copolymer before hydrogenation further includes DZ F, where F is the number average molecular weight of the chain of repeating units derived from the aromatic vinyl compound and Z or the alicyclic vinyl compound. A certain range is preferable. Specifically, DZF is preferably in the range of 1.3 or more, more preferably 1.3 or more and 8 or less, and most preferably 1.7 or more and 6 or less. When DZF is outside this range, the low birefringence of the polymer represented by the general formula (1) obtained is inferior.

[0047] The weight average molecular weight and number average molecular weight of the chain of repeating units derived from the above compound () are, for example, in the main chain of the aromatic vinyl copolymer described in the document Macromorecules 1983, 16, 1925-1928. This can be confirmed by a method of measuring the molecular weight of the aromatic bur chain extracted after reductive decomposition after adding an unsaturated double bond to ozone.

[0048] The molecular weight of the copolymer before hydrogenation is 1,000 to 1,000,000, preferably 5,000, in terms of polystyrene (or polyisoprene) equivalent weight average molecular weight (Mw) measured by GPC. ~ 500,000, more preferred <is in the range of 10,000-300,000. The weight average molecular weight (Mw) of the copolymer is too small, and the strength characteristics of the molded product of the polymer represented by the general formula (1) obtained therefrom are inferior. Inferior to sex.

[0049] Specific examples of the aromatic vinyl compound used in the above (Method 1) include, for example, styrene, α-methino styrene, α-ethino styrene, α propino styrene, α- Isopropyl styrene, a-t butyl styrene, 2-methylol styrene, 3-methyl styrene, 4-methylol styrene, 2,4-diisopropyl styrene, 2,4 dimethyl styrene, 4-t-butyl styrene, 5-t-butyl-2 —Methyl styrene, monochloro styrene, dichloro styrene, monofluoro styrene, 4-phenyl styrene, etc. are mentioned, and styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, etc. are preferable.

[0050] In the above (Method 2), specific examples of the alicyclic vinyl-based compound used include, for example, cyclobutynoleethylene, cyclopentenoethylene, cyclohexenoethylene, cycloheptylethylene, cyclohexane. Okuchiruechiren, norbornyl ethylene, hexyl ethylene dicyclohexyl, carboxymethyl Honoré ethylene to e-methylstyrene cycloalkyl, Kishinoreechire down to _a t Buchirushikuro, cyclopentenylene Honoré ethylene, hexenyl Honoré ethylene cyclohexane, Puteninoreechire down cyclohexane, cyclo OTA Saturation Le ethylene, Shikurodeke -Ruethylene, norbornylethylene, _a- methylcyclohexenylethylene, and att butylcyclohexenylethylene, and the like. Among these, cyclohexylethylene and _a- methylcyclohexylethylene are preferable.

[0051] These aromatic vinyl compounds and alicyclic vinyl compounds can be used alone or in combination of two or more.

[0052] Other monomers that can be copolymerized are not particularly limited, but chain vinyl compounds, chain conjugation compounds, and the like are used. When chain conjugation is used, operability in the production process is not limited. In addition, the polymer represented by the general formula (1) is excellent in strength properties.

[0053] Specific examples of the chain vinyl compound include, for example, ethylene, propylene, 1-butene, 1

1-Cyanoethylene (acrylonitrile), 1-ciano 1-methylethylene (methacrylonitrile), 1-cyano-1-chloroethylene ( _a -crawn acrylonitrile) -Tolyl monomers such as: 1- (Methoxycarbol)-1-Methylethylene (methacrylic acid methyl ester), 1 (Ethoxycarpyl) 1 Methylethylene (methacrylic acid ethyl ester), 1 (propoxy group 1-methylethylene (methacrylic acid propyl ester), 1 (butoxypolyol) 1 methylethylene (methacrylic acid butyl ester), 1-methoxycarbo (Meth) acrylic acid, such as -ruethylene (acrylic acid methyl ester), 1 ethoxycarbo ethylene (acrylic acid ethyl ester), 1 propoxy carbo ethylene (propyl acrylate ester), 1 butoxy carbo ethylene (butyl acrylate) Examples include ester monomers, 1 carboxyethylene (acrylic acid), 1 carboxy 1 methylethylene (methacrylic acid), unsaturated fatty acid monomers such as maleic anhydride, etc. Among them, chain olefin monomers are preferred, Propylene and 1-butene are most preferred.

[0054] Examples of the chain conjugation include 1,3 butadiene, isoprene, 2,3 dimethyl-1,3 butadiene, 1,3 pentagen, and 1,3 hexagen. Of these chain bully compounds and chain conjugate gens, chain conjugate gens are preferred, and butadiene and isoprene are particularly preferred. These chain vinyl compounds and chain conjugation gens can be used alone or in combination of two or more.

[0055] These chain vinyl compounds can be used alone or in combination of two or more.

[0056] The method for polymerizing the compound () is not particularly limited, but a batch polymerization method (batch method), a monomer sequential addition method (after starting polymerization using a part of the total amount of monomers used, And the like, and the like.) The hydrocarbon copolymer having a preferred chain structure can be obtained particularly by using the monomer sequential addition method. The copolymer before hydrogenation has a more random chain structure as the D value is smaller and as Z or DZF is larger. The degree of randomness of the copolymer is determined by the speed ratio between the polymerization rate of the aromatic vinyl compound and the polymerization rate of the other monomer that can be copolymerized. The smaller the value, the more random the chain structure.

[0057] According to the monomer sequential addition method, the uniformly mixed monomer is sequentially added into the polymerization system. Therefore, unlike the notch method, the monomer is added in the growth process by polymer polymerization. Since the polymerization selectivity can be further lowered, the resulting copolymer has a more random chain structure. In addition, since the accumulation power of the polymerization reaction heat in the polymerization system is sufficient, the polymerization temperature can be kept low and stable. [0058] For monomers incremental method, of the total amount of monomer initially, usually, from 0.01 to 60 mass ^_0/0, preferably from 0.02 to 20 weight ^_0/0, more preferably 0.05 the 10 wt ^_0/0 of the monomer to initiate polymerization by adding an initiator in a state of pre-is present in the polymerization reactor as the initial monomers. When the amount of the initial monomer is within such a range, the reaction heat generated in the initial reaction after the initiation of polymerization can be easily removed, and the resulting copolymer can be made into a more random chain structure.

[0059] When the reaction is continued until the polymerization conversion of the initial monomer is 70% or more, preferably 80% or more, more preferably 90% or more, the chain structure of the resulting copolymer becomes more random. Thereafter, the rate of force for continuously adding the remainder of the monomer is determined in consideration of the consumption rate of the monomer in the polymerization system.

[0060] Normally, when the time required for the initial monomer polymerization to reach 90% is T, and the ratio (ο / ο) of the initial monomer to all the monomers used is I, the relational expression [(100— 1) The addition of the remaining monomer is completed within a range of 0.5 to 3 times, preferably 0.8 to 2 times, more preferably 1 to 1.5 times the time given by ΧΤ / Ι]. To be determined. Specifically, the initial monomer amount and the rate of addition of the remaining monomer are determined so that it is usually in the range of 0.1 to 30 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours. Further, the total monomer polymerization conversion rate immediately after completion of the monomer addition is usually 80% or more, preferably 85% or more, and more preferably 90% or more. When the total monomer polymerization conversion rate immediately after the monomer addition is within the above range, the chain structure of the resulting copolymer becomes more random.

[0061] The polymerization reaction is not particularly limited, such as radical polymerization, ion polymerization, cationic polymerization, etc., but the polymerization operation, the ease of the hydrogenation reaction in the subsequent steps, and the hydrocarbon system finally obtained In view of the mechanical strength of the copolymer, the anion polymerization method is preferred.

[0062] In the case of radical polymerization, a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization or the like is usually used at 0 to 200 ° C, preferably 20 to 150 ° C in the presence of an initiator. However, bulk polymerization and suspension polymerization are desirable especially when it is necessary to prevent impurities from being mixed into the fat. Examples of radical initiators include benzoyl peroxide, lauryl peroxide, organic peroxides such as t-butyl-peroxy 2-ethylhexanoate, azo-isobutyl-tolyl, 4,4-azobis. 4--Cyanopentanoic acid, azodibenzoyl, etc. Water-soluble catalysts such as zo compounds, potassium persulfate, and ammonium persulfate are used as redox initiators.

Is possible.

[0063] In the case of cation polymerization, in the presence of an initiator, a temperature of usually 0 ° C to 200 ° C, preferably 20 ° C to 100 ° C, particularly preferably 20 ° C to 80 ° C. In the range, methods such as bulk polymerization, solution polymerization, and slurry polymerization can be used, but solution polymerization is preferable in consideration of removal of reaction heat. In this case, an inert solvent capable of dissolving the polymer and its hydride is used. Examples of the inert solvent used in the solution reaction include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane and cyclohexane. , Cycloaliphatic hydrocarbons such as methylcyclopentane, methylcyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene, etc., among which aliphatic hydrocarbons and alicyclic hydrocarbons are used. The solvent can be used as it is as an inert solvent for the hydrogenation reaction. These solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 10,000 parts by mass with respect to 100 parts by mass of all the monomers used.

[0064] Examples of the initiator for anion polymerization include, for example, n-butynolethium, sec-butinorelium, t-butyllithium, hexyllithium, monolithium such as lithium lithium, dilithiomethane, 1,4-dibutane, 1 Polyfunctional organolithium compounds such as 1,4-dirich-2-ethylcyclohexane can be used.

[0065] In the polymerization reaction, a polymerization accelerator or a randomizer (an additive having a function of preventing a chain of a certain component from becoming long) can be used. In the case of cation polymerization, for example, a Lewis base compound can be used as a randomizer. Specific examples of Lewis base compounds include ether compounds such as dimethyl ether, jetyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol jetyl ether, ethylene glycol methyl phenol ether, and the like.

; Tertiary amine compounds such as tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, etc .; Al-powered metal alkoxide compounds such as potassium-t-amyloxide, potassium-t-butyloxide; Triphenylphosphine And phosphine compounds such as . These Lewis base compounds can be used alone or in combination of two or more.

[0066] The polymer obtained by the above-described radical polymerization and cation polymerization can be recovered by a known method such as a steam stripping method, a direct desolvation method, or an alcohol coagulation method. In addition, when an inert solvent is used in the hydrogenation reaction during the polymerization, the polymer is not recovered from the polymerization solution and can be used as it is in the hydrogenation step.

[0067] Hereinafter, the method for hydrogenating unsaturated bonds will be described in more detail.

[0068] Unsaturated carbon such as aromatic ring or cycloalkene ring of copolymer before hydrogenation Carbon When performing hydrogenation reaction such as double bond or unsaturated bond of main chain, reaction method, reaction form However, a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction is preferred. For example, in an organic solvent, Nickel, cobalt, iron, titanium, rhodium, noradium, platinum, ruthenium, and rhenium power. A method using a catalyst containing at least one metal selected from the group consisting of metals. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used.

[0069] The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the support include activated carbon, silica, alumina, calcium carbide, titer, magnesia, zirconia, diatomaceous earth, silicon carbide and the like. The supported amount of the catalyst is usually 0.01 to 80% by mass, preferably The range is from 0.05 to 60% by mass. Homogeneous catalysts are catalysts that combine nickel, cobalt, titanium or iron compounds with organometallic compounds (eg organoaluminum compounds, organolithium compounds), or organometallics such as rhodium, rhodium, platinum, ruthenium, rhenium Complex catalysts can be used. As the nickel, cobalt, titanium, or iron compound, for example, acetyl acetone salt, naphthene salt, cyclopentagenyl compound, cyclopentagel dichroic compound of various metals and the like are used. As the organoaluminum compound, alkyl aluminum such as triethylaluminum and triisobutylaluminum, aluminum halide such as jetylaluminum chloride and ethylaluminum dichloride, alkylaluminum hydride such as diisobutylaluminum halide and the like are preferably used. . [0070] Examples of the organic metal complex catalyst, each of the above metal γ- dichloro _π benzene complex, dichloro one tris (bird whistle - Le phosphine) complexes, hydride one black port one bird whistle - Ruhosufi down metal complexes such as complexes used Is done. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount used is usually from 0.01 to LOO on a mass basis relative to the polymer. Parts, preferably 0.05 to 50 parts, more preferably 0.1 to 30 parts.

[0071] The hydrogenation reaction is preferably performed at a temperature of 10 ° C to 250 ° C, preferably 50 ° C because the hydrogenation rate can be increased and the polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction can be reduced. C to 200 ° C, more preferably 80 ° C to 180 ° C. The hydrogen pressure is usually 0. IMPa to 30 MPa. In addition to the above reasons, from the viewpoint of operability, it is preferably lMPa to 20 MPa, more preferably 2 MPa to: LOMPa.

[0072] The hydrogenation rate of the hydride obtained in this manner is determined by iH-NMR as follows: main chain carbon-carbon unsaturated bond, aromatic ring carbon-carbon double bond, unsaturated ring carbon carbon All of the double bonds are usually 90% or more, preferably 95% or more, more preferably 97% or more. When the hydrogenation rate is low, the low birefringence, thermal stability, etc. of the resulting copolymer are lowered.

[0073] The method for recovering the hydride after completion of the hydrogenation reaction is not particularly limited. Usually, after removing the hydrogenation catalyst residue by a method such as filtration or centrifugation, the solution power solution of the hydride is directly removed by drying, the hydride solution is poured into a poor solvent for the hydride, A method of solidifying the hydride can be used.

[0074] << Mixing of thermoplastic plastic resin and inorganic fine particles >>

The composite material that is a raw material of the optical element of the present invention is a composite material obtained by adding inorganic particles to a thermoplastic resin resin that is being melted (hereinafter also simply referred to as thermoplastic resin or resin) and kneading. Preferred is a production method for producing a material (melt kneading method) or a production method for a composite material in which a resin dissolved in a solvent and inorganic particles are mixed and then the organic solvent is removed.

[0075] In the present invention, it is particularly desirable that the composite material is produced by a melt-kneading method. Polymerize thermoplastic resin in the presence of inorganic particles or produce inorganic particles in the presence of thermoplastic resin However, it is because special conditions are required in the polymerization of resin and the production of inorganic particles. In the melt-mixing method, composite materials can be produced by mixing inorganic particles of coconut resin produced by an existing method, so that it is usually possible to produce inexpensive composite materials.

[0076] An organic solvent can also be used for melt kneading. By using an organic solvent, the temperature of melt kneading can be lowered, and the deterioration of the resin can be easily suppressed. In that case, it is preferable to perform devolatilization after melt-kneading to remove the organic solvent from the composite material.

[0077] As an apparatus that can be used for melt-kneading, a closed kneading apparatus or a notch-type kneading apparatus such as a lab plast mill, a Brabender, a Bannolly mixer, an adder, a roll, and the like can be given. It can also be produced using a continuous melt-kneading apparatus such as a single-screw extruder or a twin-screw extruder.

[0078] As a specific method of mixing the treated particles and thermoplastic resin, KRC Ader (manufactured by Kurimoto Iron Works); Polylab System (manufactured by HAAKE); Nanocon mixer (Toyo) Seita Seisakusho Co., Ltd.); Nauta Mixer Bus "Co" Ader (Buss Co.); TEM Extruder (Toshiba Machine Co., Ltd.); TEX twin screw kneader (Nippon Steel Works Co., Ltd.); Iron rolls); Three roll mills, mixing roll mills, Ader (Inoue Seisakusho);-Dettas (Mitsui Mining Co.); MS pressurizer-1 Dader, Niida Ruder (Moriyama Seisakusho); One mixer (manufactured by Kobe Steel) is listed.

[0079] When the melt kneading is used in the method for producing a thermoplastic resin material of the present invention, the thermoplastic resin and inorganic particles may be added and kneaded in one batch, or divided stepwise. It may be added and kneaded. In this case, in a melt-kneading apparatus such as an extruder, it is possible to add components to be added step by step from the middle of the cylinder. However, when heating the resin in a molten mixture, it is preferable to first add a material that prevents thermal degradation of the resin, such as an acid inhibitor. When inorganic particles are added thereafter, the temperature of melt-kneading is often increased, and the deterioration of the resin becomes remarkable without an antioxidant. On the other hand, light stabilizers are often colored due to thermal degradation. For this reason, in the melt-mixing process, it is preferable to carry out addition at a later step as much as possible. Therefore, at least a part is added after the addition of inorganic particles.

[0080] In the present invention, when the composite kneading is performed by melt kneading, the inorganic particles are powdery! It can be added as it is. Alternatively, it can be added in a dispersed state in the liquid. When adding in the state disperse | distributed in the liquid, it is preferable to perform devolatilization after kneading | mixing.

[0081] When added in a dispersed state in the liquid, it is preferable to add the agglomerated particles dispersed in the primary particles in advance. Various dispersing machines can be used for dispersion, but a bead mill is particularly preferable. There are various kinds of beads, but small ones are preferred. Particularly, beads having a diameter of 0.1 mm or less and 0.001 mm or more are preferred.

[0082] Inorganic particles are preferably added in a surface-treated state. However, there is a method such as an integral blend in which a surface treatment agent and inorganic particles are added simultaneously to form a composite with a resin. It is also possible to use various methods.

[0083] << Method for Producing Optical Resin Lens >>

Next, a method for producing an optical resin lens that is one of the optical elements of the present invention will be described.

[0084] The optically-absorbent lens according to the present invention is prepared first by preparing an irrigation composition (in some cases, oleum alone or in a mixture of rosin and additives). Forming a prepared rosin composition.

[0085] The optical fiber lens according to the present invention is prepared by first preparing a resin composition (the resin may be a resin alone or a mixture of a resin and an additive), and then obtained. Forming a prepared rosin composition.

[0086] The molded product of the thermoplastic resin material of the present invention is obtained by forming a molding material comprising the resin composition. The molding method is not particularly limited, but melt molding is preferred in order to obtain a molded product having excellent characteristics such as low birefringence, mechanical strength, and dimensional accuracy. Examples of the melt molding method include commercially available press molding, commercially available extrusion molding, and commercially available injection molding. Injection molding is also preferable in terms of moldability and productivity.

[0087] The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, a resin composition in injection molding (in the case of a resin alone or in a mixture of a resin and an additive) The temperature of the resin imparts appropriate fluidity to the resin during molding to prevent sink marks and distortion of the molded product, prevents the occurrence of silver streaks due to thermal decomposition of the resin, and further, the yellowing of the molded product From the viewpoint of effectively preventing the temperature, the range of 150 ° C to 400 ° C is preferable, more preferably 200 ° C to 350 ° C, and particularly preferably 200 ° C to 330 ° C. .

[0088] The molded product according to the present invention can be used in various forms such as a spherical shape, a rod shape, a plate shape, a cylindrical shape, a tubular shape, a tubular shape, a fibrous shape, a film or a sheet shape, and has a low birefringence. Because of its excellent properties, transparency, mechanical strength, heat resistance, and low water absorption, it is used as an optical resin lens that is one of the optical elements of the present invention, but is also suitable as other optical components.

[0089] Optical resin lens

The optical resin lens according to the present invention can be obtained by the above-described production method. Specific examples of application to optical components are as follows.

[0090] For example, as an optical lens or an optical prism, an imaging lens of a camera; a lens such as a microscope, an endoscope or a telescope lens; an all-light transmission lens such as a spectacle lens; CD, CD-ROM, WORM Type optical disc), MO (rewritable optical disc; magneto-optical disc), MD (mini disc), DVD (digital video disc) and other optical disc pick-up lenses; laser beam printer f Θ lenses, sensor lenses, etc. Laser scanning system lens; prism lens for camera finder system.

[0091] Optical disc applications include CD, CD-ROM, WORM (recordable optical disc), MO (rewritable optical disc; magneto-optical disc), MD (mini disc), DVD (digital video disc), etc. It is done. Other optical applications include light guide plates such as liquid crystal displays; optical films such as polarizing films, retardation films, and light diffusing films; light diffusing plates; optical cards; and liquid crystal display element substrates.

Example

[0092] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0093] «Preparation of greaves material»

By using a polylab system (manufactured by HAAKE) to melt and knead the following particles in an amount of 20% by volume with respect to the following resin, an inorganic / organic composite thermoplastic material containing 20% by volume of particles is obtained. Obtained.

[0094] The details of the materials listed in Table 1 are as follows. [0095] APL5014DP: manufactured by Mitsui Chemicals, APL5014 (the above two applicable compounds) Water absorption: 0.05% by mass ''

ZEONEX 3S0R: manufactured by ZEON Co., Ltd. (cyclic olefin-based polymer) (2 above-mentioned corresponding compounds) Water absorption: 0.01% by weight%

Teijin Panlite AD5503: Teijin Limited (Polycarbonate resin)

Water absorption 0.2%-Silica: Nippon Aerosil RX300 Average particle size 7ran

Alumina: TM-300 (y alumina) manufactured by Daimei Chemical Co., Ltd. Average particle size: 7 nm Stearic acid: manufactured by Wako Pure Chemical Industries, Ltd.

[0096] [Chemical 4]

APL5014DP ZEONEX 330R

70,000

n: equimolar weight average molecular weight 30,000

[0097] << Production of Optical Element >>

The obtained composite material was pressed under reduced pressure of 160 ° C and 13.3 Pa to obtain a molded product of Φ ΐ1πιπι and thickness of 3 mm (however, the hardness sample was Φ30πιπι and thickness of 6 mm was prepared) The surface was polished to produce an optical element, which was designated as Example and Comparative Sample No. 19 according to the present invention. These were used for the following optical property measurements.

[0098] << Evaluation of optical element >>

Optical element water absorption

The obtained sample was placed in an 85 ° C dry environment (0% RH) for 3 days and weighed (the obtained value is A gram), then placed at 60 ° C and 90% RH for 3 weeks and weighed. (The obtained value is B-gram). The water absorption rate of the optical element was calculated by the following formula.

[0099] Water absorption of optical element = (B-A) / A 100

Difference paper (Rule 26) (crack)

The obtained sample was placed at 85 ° C. and 90% RH for 48 hours, allowed to stand at room temperature for 3 hours and then observed visually and magnified 100 times with an optical microscope, and evaluated as follows.

[0100] ○: No cracks are observed

X: There is a crack.

[0101] (Coloring during molding)

Each melt composition was melted and heat-molded, and the following evaluation was made visually.

[0102] ○: Coloring is not recognized

X: Coloring is recognized.

[0103] (Change in refractive index dnZdT)

Using the obtained sample, an automatic refractometer (Karuyu Kogyo Co., Ltd .: KPR-2200) using the minimum deviation method, the measurement temperature was changed at 25 ° C and the temperature was changed by 60 ° C, and the refractive index was changed. The refractive index change rate dnZdT was measured, and the temperature dependence of the refractive index was evaluated according to the following criteria.

[0104] Absolute value power of DnZdT 0 or more, if 9. OX 10- ⁵ or less, a practical range is widened, 9.

If you are beyond the OX 10_ ⁵ is the current equivalent.

[0105] (Hardness (Rockwell hardness))

Measured by a method based on JIS K7202-2, and the Rockwell hardness was determined by the following relational expression.

[0106] HR = 130— e

HR: Rockwell hardness

e: Depth of indentation after removal of test weight, expressed as 0.002 mm as a unit. The following evaluation was performed from the obtained HR.

[0107] A: 90 or more

B: Less than 90

[0108] [Table 1] Optical element

Sample Particle size Crack Molding

Resin water absorption rate of inorganic fine particles Hardness Remarks

No. (nm) (85 ° C 90% 48h) coloring

Hidden%)

1 APL5014DP Silica 7 0.16 ○ ○ -8.5 A The present invention

2 ZE0NEX33OE silica 7 0.13.

3 APL5014DP Alumina 7 0.6 ○ ○ -8 A The present invention

4 ZE0NEX33OR Alumina 7 0.5 ○ ○ -9.7 A The present invention

5 APL5014DP ― One 0.05 X ○ --11.8 B Comparative example

6 ZE0NEX33OE-One 0.01 X ○ -12.3 B Comparative example

7 APL5014DP Stearic acid-0.01 ○ X -11.8 B Comparative example

8 AD5503 Silica 7 0.39 ○ ○ One 10.7 B Comparative example

9 AD5503 Alumina 7 0.8 ○ ○ -9.7 B Comparative example

From Table 1, it can be seen that all the samples of the present invention are optical devices that have improved hardness for coloring due to thermal decomposition during molding with few moisture absorption cracks, and a small change in refractive index with respect to temperature. .

Replacement paper (mi 26)

Claims

Claims: A thermoplastic resin material in which inorganic fine particles having an average particle size of 1.0 to 30 rmi are dispersed in a thermoplastic resin having a water absorption of 0.05% by mass or less is molded. A featured optical element. 2. The optical element according to claim 1, wherein the thermoplastic plastic resin also has a polymer force represented by the following general formula (1).

[Chemical 1]

(Wherein x and y are copolymerization ratios and are real numbers satisfying 50 / 50≤y / x≤95Z5, n is the number of substituents Q, and is an integer of 0≤n≤2. R ¹ is a hydrocarbon group group force of 2 to 20 carbon atoms, and ^one or more 2 + n-valent groups selected. R ² is a hydrogen atom and carbon / hydrogen force or carbon number. 1 or more selected from a structural group of 1 to 10 and a monovalent group of 2 or more, and R ³ is a hydrocarbon group having 2 to 10 carbon atoms. Q is COOR ⁴ (R ⁴ is a hydrogen atom and carbon 'hydrogen, one kind selected from the structure group consisting of 1 to 10 carbon atoms! /, And two or more monovalents. 1 type or 2 or more types of divalent groups selected from the structural group represented by:

3. The optical element according to claim 1, wherein the optical element is an inorganic fine particle force S, a fine oxide particle of aluminum oxide, or an fine particle of aluminum oxide.

The optical element according to any one of claims 1 to 3, wherein the inorganic fine particles are subjected to a surface hydrophobization treatment.

An optical resin lens according to any one of claims 1 to 4, wherein the optical element force according to any one of claims 1 to 4 is provided. Replacement paper (Rule 2S)