Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B13/00—Optical objectives specially designed for the purposes specified below
  • G02B13/18—Optical objectives specially designed for the purposes specified below with lenses having one or more non-spherical faces, e.g. for reducing geometrical aberration

Definitions

• the present invention relates to an optical lens made of thermoplastic polymer, an optical system unit including the optical lens, and an optical device using the optical system unit .
• An optical lens formed of a transparent plastic material such as acrylic resin or PMMA is used in various optical devices.
• conventional plastic materials usable for production of the optical lenses have defects such as a refractive index cannot be increased to a high value and a focal length varies according to changes in the refractive index with temperature.
• nanocomposite materials organic-inorganic hybrid materials
• a nanocomposite material disclosed in Japanese Patent Laid-Open Publication No. 2005-055852 is prepared by dispersing niobium oxide (Nb 2 Os) having a maximum length (particle diameter) of 30 nm into a transparent plastic matrix.
• the refractive index of this nanocomposite material cannot be increased to a high value
• the nanocomposite material offsets a reduction in the refractive index of the plastic matrix by an increase in the refractive index of the inorganic fine particles as the temperature increases. Accordingly, variations in the total refractive index are prevented.
• the maximum length of the niobium oxide to be dispersed is preferably 20 nm, and more preferably within a range of 10 nm to 15 nm to prevent a significant reduction in optical transmittance.
• the inorganic fine particles having the particle diameter of approximately 30 nm have no practical utility.
• the upper practical size limit for the particle diameter is 15 nm. It is more preferable that the particle diameter is at most 10 nm. It is furthermore preferable that the particle diameter is at most 7 nm.
• an object of the present invention is to provide an optical lens having uniform transmittance properties, a uniform refractive index profile, and excellent optical properties although the optical lens is made of a nanocomposite material in which inorganic fine particles are dispersed into a plastic matrix for the purpose of achieving a high refractive index and improving temperature properties.
• Another object of the present invention is to provide an optical system unit and an optical device including the optical lens.
• an optical lens of the present invention is produced from a nanocomposite material (organic-inorganic hybrid material) having the following specific structure.
• a thermoplastic polymer (thermoplastic) having a functional group, in a main chain end or a side chain, capable of forming a chemical bond with at least one of the inorganic fine particles is used.
• the functional group is bonded to the inorganic fine particle and thereby the main chain is bonded to the inorganic fine particle.
• Each inorganic fine particle is surrounded with the main chains, so that a space is kept between the inorganic fine particles.
• the inorganic fine particles are homogeneously dispersed in the plastic matrix.
• An optical lens made of such nanocomposite material exhibits excellent optical properties such as high optical transmittance and uniform refractive index.
• the optical lens made of the nanocomposite material having the above-described specific structure is resistant to heat, and softening and deformation rarely occur by heat when compared to the conventional plastic lens. Accordingly, although the optical lens is made of plastic, the optical lens of the present invention can be used in a location having wide temperature variations.
• the optical lens is stably mass-produced by exploiting the thermoplastic characteristic of the plastic lens, through injection molding or press forming using a mold having a spherical or a nonspherical surface, resulting in low production cost. It is also possible to make the refractive index to be at least 1.65 by appropriately selecting the plastic matrix and inorganic fine particles.
• the optical lens or the optical system unit according to the present invention is applicable in various optical devices, such as an imaging device, an image projection device, an optical measuring device.
• the optical lens made of the above-described nanocomposite material has significantly high transparency, uniform refractive index profile, and excellent optical properties when compared to the optical lens made of the conventional nanocomposite material. Since the size of the inorganic fine particles which affects adjustment of the refractive index is smaller and the inorganic fine particles are more homogeneously dispersed in the plastic matrix than the conventional inorganic fine particles, the above-described nanocomposite material exhibits a compensation effect more capable of following temperature changes in suppressing variations of refractive index with temperature.
• Figure 1 is a graph showing a correlation between a particle diameter of inorganic fine particles and optical transmittance when fine particles of nano-order are dispersed into a plastic matrix;
• Figure 2 is an external view of a mobile phone with a built-in digital camera
• Figure 3 is a block diagram of lenses according to a first embodiment of the present invention
• Figure 4 is an aberration diagram of the first embodiment
• Figure 5 is a block diagram of lenses according to a second embodiment of the present invention.
• Figure 6 is an aberration diagram of the second embodiment;
• Figure 7 is a block diagram of lenses according to a third embodiment of the present invention.
• Figure 8 is an aberration diagram of the third embodiment.
• thermoplastic polymer (thermoplastic) effectively used for production of an optical lens of the present invention has a functional group, in at least one of a main chain end and a side chain, capable of forming any kind of chemical bond with inorganic fine particles.
• thermoplastic polymer include:
• thermoplastic polymer having at least one of functional groups in a side chain, and such functional group is selected from the following:
• R 11 , R 12 , R 13 , and R 14 can be any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group] , -SO 3 H, -OSO 3 H, -CO 2 H, and -Si (OR 15 ) m iR 16 3 -mi [each of R 15 and R 16 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, and ml is an integer from 1 to 3] ;
• thermoplastic polymer having at least one of functional groups in at least a part of a main chain end, and such functional group is selected from the following,
• R 21 , R 22 , R 23 , and R 24 can be any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group] , -SO 3 H, -OSO 3 H, -CO 2 H, and -Si (OR 25 ) ⁇ 26 ⁇ [each of R 25 and R 26 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, and m2 is an integer from 1 to 3] ; and
• thermoplastic polymers (1) to (3) are detailed.
• the thermoplastic polymer (1) used in the present invention has a functional group, in a side chain, capable of forming a chemical bond with inorganic fine particles.
• the "chemical bond” used herein includes, for example, a covalent bond, an ionic bond, a coordinate bond, and a hydrogen bond.
• each functional group may form a different chemical bond with inorganic fine particles. Whether a functional group is capable of forming a chemical bond with inorganic particles is determined by the presence of a chemical bond between the functional group and the inorganic fine particles when the thermoplastic polymer and the inorganic fine particles are dispersed in an organic solvent. All or a part of the functional groups of the thermoplastic polymer may form chemical bonds with inorganic fine particles.
• the functional group capable of forming the chemical bond with the inorganic fine particles stably disperses the inorganic fine particles in the thermoplastic polymer by forming the chemical bond with the inorganic fine particles.
• Such functional group is selected from
• R 11 , R 12 , R 13 , and R 14 can be any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group] , -SO 3 H, -OSO 3 H, -CO 2 H, or -Si (OR 15 ) m iR 16 3 _ m i [each of R 15 and R 16 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, and ml is an integer from 1 to 3] .
• the alkyl group has preferably from one to 30 carbon atoms, and more preferably from one to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.
• the substituted alkyl group includes, for example, an aralkyl group.
• the aralkyl group has preferably from 7 to 30 carbon atoms, and more preferably from 7 to 20 carbon atoms, and examples thereof include a benzyl group, and a p-methoxybenzyl group.
• the alkenyl group has preferably from 2 to 30 carbon atoms, and more preferably from 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group.
• the alkynyl group has preferably from 2 to 20 carbon atoms, and more preferably from 2 to 10 carbon atoms, and examples thereof include an ethynyl group, and a 2-phenylethynyl group.
• the aryl group has preferably from 6 to 30 carbon atoms, and more preferably from 6 to 20 carbon atoms, and examples thereof include a phenyl group, a 2, 4, 6-tribromophenyl group, and a 1-naphthyl group.
• the aryl group used herein includes a heteroaryl group.
• substituents for the alkyl group, the alkenyl group, the alkynyl group, and the aryl group include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom) and an alkoxy group (for example, a methoxy group and an ethoxy group) in addition to the above-described alkyl group, the alkenyl group, the alkynyl group, and the aryl group.
• Preferable number of carbon atoms, functional groups, and substituents for the R 15 and R 16 are the same as those for R 11 , R 12 , R 13 and R 14 .
• the ml is preferably 3.
• thermoplastic polymer used in the present invention is a copolymer having a repeating unit represented by a general formula (1) below.
• Such copolymer is synthesized by copolymerization of vinyl monomers represented by a general formula (2) below.
• R represents one of a hydrogen atom, a halogen atom, and a methyl group.
• X represents a bivalent linking group selected from a group consists of -CO 2 -, -OCO-, -CONH-, -OCONH-, -OCOO-, -0-, -S-, -NH-, and a substituted or unsubstituted arylene group. It is more preferable that "X” is -CO 2 - or a p-phenylene group.
• "Y” represents a bivalent linking group having 1 to 30 carbon atoms. The number of the carbon atoms is preferably 1 to 20, more preferably 2 to 10, and furthermore preferably 2 to 5.
• an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an arylene group, an aryleneoxy group, an aryleneoxycarbonyl group, and a combination of the above groups may be used.
• the alkylene group is preferable.
• “q” represents an integer from zero to 18. It is more preferable that “q” is an integer from zero to 10. It is furthermore preferable that “q” is an integer from zero to 5. It is especially preferable that "q" is zero or one.
• Z represents a functional group selected from a group consists of
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and ml are the same as those of the R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and ml previously described, except that each of R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 is a hydrogen atom or an alkyl group.
• compounds having one addition-polymerizable unsaturated bond selected from styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, dialkyl itaconates, and dialkyl esters or monoalkyl esters of fumaric acid, can be exemplified.
• styrene derivative examples include styrene, 2, 4, 6-tribromostyrene, 2-phenylstyrene.
• acrylic esters examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, and tetrahydrofurfuryl acrylate.
• methacrylic esters examples include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate,
• 2-hydroxyethyl methacrylate trimethylolpropane monomethacrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate .
• acrylamides examples include acrylamide, N-alkyl acrylamide (with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group) , N,N-dialkyl acrylamide (with an alkyl group having 1 to 6 carbon atoms) , N-hydroxyethyl-N-methyl acrylamide and N-2-acetamideethyl-N- acetyl acrylamide.
• N-alkyl acrylamide with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group
• N,N-dialkyl acrylamide with an alkyl group having 1 to 6 carbon atoms
• N-hydroxyethyl-N-methyl acrylamide and N-2-acetamideethyl-N- acetyl acrylamide.
• methacrylamides examples include methacrylamide, N-aklyl methacrylamide (with an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, or a propyl group) , N,N-dialkyl methacrylamide (with an alkyl group having 1 to 6 carbon atoms) , N-hydroxyethyl-N-methyl methacrylamide and N-2-acetamideethyl-N-acetyl methacrylamide .
• allyl compounds examples include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate), and allyl oxyethanol .
• allyl esters for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate
• allyl oxyethanol examples include allyl esters (for example, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate), and allyl oxyethanol .
• vinyl ethers examples include alkyl vinyl ethers with an alkyl group having 1 to 10 carbon atoms, such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, l-methyl-2, 2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether and tetrahydrofurfuryl vinyl ether.
• alkyl vinyl ethers with an alkyl group having 1 to 10 carbon atoms such as hexyl vinyl ether, octyl vinyl
• vinyl esters examples include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl pivalate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate, vinyl- ⁇ -phenyl butylate and vinyl cyclohexyl carboxylate .
• dialkyl itaconates examples include dimethyl itaconate, diethyl itaconate and dibutyl itaconate.
• dialkyl esters or monoalkyl esters of the fumaric acid examples include dibutyl fumarate.
• the thermoplastic polymer (1) used in the present invention has a number average molecular weight of preferably from 1,000 to 500, 000, more preferably from 3, 000 to 300, 000, and especially preferably from 10,000 to 100,000. Where the number average molecular weight of the thermoplastic polymer (1) is at most 500,000, processability of the thermoplastic polymer (1) improves, and where it is at least 1,000, mechanical strength increases.
• the "number average molecular weight" used herein is a polystyrene equivalent molecular weight based on detection by a differential refractometer of a GPC analyzer with columns of TSK gel GMHxL, TSK gel G4000HxL, and TSK gel G2000HxL (trade names of Tosoh Corporation) using tetrahydrofuran as a solvent.
• the average number of the functional group that bonds to the inorganic fine particles per main chain is preferably from 0.1 to 20, more preferably from 0.5 to 10, and especially preferably from 1 to 5. Where the average number of the functional group is at most 20 per main chain, gelation and an increase in viscosity in a solution state caused by coordination of the thermoplastic polymer (1) to plural inorganic fine particles is prevented. Where the average number of the functional group per main chain is at least 0.1, the inorganic fine particles are dispersed stably.
• a glass transition temperature of the thermoplastic polymer (1) used in the present invention is preferably 80 0 C to 400 0 C, and more preferably 130 0 C to 380 0 C.
• An optical component having sufficient heat resistance is produced from a polymer having the glass transition temperature of at least 80 0 C. Processability of the polymer is improved by using the polymer having the glass transition temperature of at most 400 0 C.
• the refractive index of the thermoplastic polymer (1) is approximately 1.48
• the transparent molded product having the refractive index in a level of 1.60 can be provided.
• the refractive index of the thermoplastic polymer (1) used in the present invention is preferably at least 1.55, and more preferably at least 1.58. These refractive indices are measured at 589 nm wavelength at 22 0 C.
• thermoplastic polymer (1) used in the present invention has a light transmittance of preferably at least 80%, more preferably at least 85%, and especially preferably at least 88%, at 589 nm wavelength with the thickness of 1 mm.
• thermoplastic polymer (1) that can be used in the present invention
• thermoplastic polymer that can be used in the present invention is not limited to the following examples.
• the thermoplastic polymer (1) may be one kind or a mixture two or more kinds of the above-mentioned thermoplastic polymers .
• the thermoplastic polymer (1) may be mixed with a thermoplastic polymer (2) and/or a thermoplastic polymer (3) .
• the thermoplastic polymer (2) used in the present invention has a functional group, in at least a part of a main chain end, capable of forming a chemical bond with inorganic fine particles.
• the functional group may be present in one or both of the main chain ends. However, it is preferable that the functional group is present only in one of the main chain ends. Plural functional groups may be present in the main chain end.
• the "main chain end” refers to a moiety of the polymer excluding a repeating unit and a structure sandwiched between repeating units.
• the "chemical bond” is considered similar to that in the above-described thermoplastic polymer (1) .
• the functional group capable of forming a chemical bond with inorganic fine particles is a selected one of
• R 21 , R 22 , R 23 , and R 24 can be any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group] , -SO 3 H, -OSO 3 H, -CO 2 H, and -Si (OR 25 ) H12 R 2 VnU!
• each of R 25 and R 26 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group, and m2 is an integer from 1 to 3] .
• R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, preferable number of carbon atoms, functional groups, and substituents for R 21 , R 22 , R 23 , R 24 , R 25 , and R 26 are the same as those for R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 . It is preferable that m2 is 3.
• thermoplastic polymer (2) in the present invention is not particularly limited.
• a well known polymer structure such as that of poly (meth) acrylic ester, polystyrene, polyvinyl carbazole, polyarylate, polycarbonate, polyurethane, polyimide, polyether, polyether sulfone, polyether ketone, polythioether, cycloolefin polymer, and cycloolefin copolymer can be employed.
• a vinyl polymer, a polyarylate and an aromatic group-containing polycarbonate are preferable, and a vinyl polymer is more preferable. Specific examples are the same as those described for the thermoplastic polymer (1) .
• the thermoplastic polymer (2) used in the present invention has a refractive index of preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and especially preferably 1.65 or more.
• the refractive index used herein is measured using an Abbe' s refractometer (a product of Atago, Model : DR-M4) with incident light of 589 nm wavelength.
• the thermoplastic polymer (2) used in the present invention has a glass transition temperature of preferably from 50 0 C to 400 0 C, and more preferably from 80 0 C to 380°C. Where the thermoplastic polymer (2) has a glass transition temperature of at least 50 0 C, heat resistance increases. Where the thermoplastic polymer (2) has a glass transition temperature of at most 400 0 C, processing becomes facilitated.
• thermoplastic polymer (2) used in the present invention has a light transmittance of preferably at least 80%, and more preferably at least 85%, at 589 nm wavelength with the thickness of 1 mm.
• the thermoplastic polymer (2) used in the present invention has a number average molecular weight of preferably from 1,000 to 500, 000.
• the number average molecular weight is preferably from 3, 000 to 300, 000, and more preferably from 5, 000 to 200, 000, and especially preferably from 10, 000 to 100, 000.
• mechanical strength increases.
• processability of the thermoplastic polymer (2) improves.
• a method of introducing the functional group into the main chain end is not particularly limited.
• the functional group may be introduced at the time of polymerization, or after polymerization.
• the functional group is introduced after polymerization, the polymer is isolated and then subjected to terminal functional group transformation or main chain decomposition.
• polymer reactions such as a method of synthesizing polymer by polymerization using an initiator, a terminator, a chain transfer agent or the like having a functional group and/or a protected functional group, and a method in which a phenol terminal group of polycarbonate synthesized from, for example, bisphenol A is modified with a reacting agent containing a functional group.
• radical polymerization of vinyl monomer by a chain transfer method using a sulfur-containing chain transfer agent described in pages 110-112 of "New Polymer Experimental Studies 2, Synthesis and Reaction of Polymer (1) Synthesis of Addition-Type Polymer” edited by the Society of Polymer Science, Japan; living cationic polymerization using a functional group-containing initiator and/or a functional group-containing terminator, described in pages 255-256 "New Polymer Experimental Studies 2, Synthesis and Reaction of Polymer (1) Synthesis of Addition-Type Polymer” edited by the Society of Polymer Science, Japan; and ring-opening metathesis polymerization using a sulfur-containing chain transfer agent, described in pages 7020-7026 of Macromolecules, vol. 36, (2003) can be exemplified.
• thermoplastic polymer Preferable specific examples of the thermoplastic polymer
• thermoplastic polymer (2) that can be used in the invention are described in the following illustrated compounds P-I to P-22, but the thermoplastic polymer
• thermoplastic polymers (2) may be used. These thermoplastic polymers (2) may contain other copolymerization components .
• thermoplastic polymer (3) used in the present invention is a block copolymer composed of a hydrophobic segment (A) and a hydrophilic segment (B) .
• the hydrophobic segment (A) makes up the polymer that is not soluble in water nor methanol.
• the hydrophilic segment (B) makes up the polymer soluble in at least one of water and methanol.
• Types of the block copolymer include AB type, B 1 AB 2 type, and A 1 BA 2 type. In the B 1 AB 2 type, two hydrophilic segments B 1 and B 2 may ⁇ be the same or different. In the A 1 BA 2 type, two hydrophobic segments A 1 and A 2 may be the same or different. In view of dispersibility, the block copolymers of the AB type or the A 1 BA 2 type are preferable. In view of production suitability, the AB type or the ABA type (the A 1 BA 2 type in which the two hydrophobic segments A 1 and A 2 are the same) is preferable, and the AB type is especially preferable.
• Each of the hydrophobic segment (A) and the hydrophilic segment (B) may be selected from well known polymers such as vinyl polymer obtained by polymerization of vinyl monomers, polyether, ring-opening metathesis polymerization polymer and condensation polymer (polycarbonate, polyester, polyamide, polyether ketone, polyether sulfone, and the like) .
• vinyl polymer, ring-opening metathesis polymerization polymer, polycarbonate, and polyester are preferable. In view of production suitability, vinyl polymer is more preferable.
• vinyl monomer (a) forming the hydrophobic segment (A) examples include the following: acrylic esters, methacryl esters (an ester group is a substituted or unsubstituted aliphatic ester group or a substituted or unsubstituted aromatic ester group, for example, a methyl group, a phenyl group, a naphthyl group, or the like) ; acryl amides, methacryl amides, more specifically, N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides, N-disubstituted methacrylamides (substituents of a monosubstitution product and disubstitution product include a substituted or unsubstituted aliphatic group, and a substituted or unsubstituted aromatic group, for example, a methyl group, a phenyl group, a naphthyl group,
• Acrylic esters and methacrylic esters whose ester group is substituted or unsubstituted aromatic group; and styrenes are more preferable.
• Examples of the vinyl monomer (b) forming the hydrophilic segment (B) include the following: acrylic acid, methacrylic acid, acrylic esters and methacrylic esters having a hydrophilic substituent at an ester moiety; styrenes having a hydrophilic substituent at an aromatic ring; vinyl ethers, acrylamides, methacryl amides, N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides, and N-disubstituted methacrylamides having a hydrophilic substituent .
• the hydrophilic substituent preferably has a functional group selected from a group consists of
• R 31 , R 32 , R 33 , and R 34 can be any of a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group] , -SO 3 H, -OSO 3 H, -CO 2 H, -OH, and -Si (OR 35 ) m3 R 36 3 - m3 [each of R 35 and R 36 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, and m3 is an integer from 1 to 3] .
• R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, or a substituted or unsubstituted aryl group, preferable number of carbon atoms, functional groups, and substituents for R 31 , R 32 , R 33 , R 34 , R 35 , and R 36 are the same as those for R 11 , R 12 , R 13 , R 14 , R 15 , and R 16 .
• the m3 is preferably 3.
• the functional group is preferably
• the block copolymer has a functional group selected from [Chemical formulae 34]
• a content of the functional group is at least 0.05 ⁇ imol/g and at most 5.0 mmol/g.
• the hydrophilic segment (B) is preferably acrylic acid, methacrylic acid, acrylic ester or methacrylic ester with a hydrophilic substituent at the ester moiety, and styrene having a hydrophilic substituent in an aromatic ring.
• the hydrophobic segment (A) formed of the vinyl monomer (a) may also contain the vinyl monomer (b) within a range of not changing the hydrophobic property. It is preferable that a molar ratio between the vinyl monomer (a) and the vinyl monomer (b) contained in the hydrophobic segment (A) is 100:0 to 60:40.
• the hydrophilic segment (B) formed of the vinyl monomer (b) may also contain the vinyl monomer (a) within a range of not changing the hydrophilic property. It is preferable that a molar ratio between the vinyl monomer (b) and the vinyl monomer (a) contained in the hydrophilic segment (B) is 100:0 to 60:40.
• Each of the vinyl monomers (a) and (b) may be composed of one kind or two or more kinds of monomers.
• the vinyl monomers (a) and (b) are selected in accordance with the purpose (for example, to adjust acid content, to adjust glass transition temperature (Tg) , to adjust solubility in organic solvent or water, or to adjust dispersion stability) .
• a content of the functional group relative to the total amount of the block copolymer is preferably 0.05 mmol/g to 5.0 mmol/g, and more preferably, 0.1 mmol/g to 4.5 mmol/g, and especially preferably 0.15 mmol/g to 3.5 mmol/g. Where the content of the functional group is too low, dispersion suitability may be reduced. Where the content of the functional group is too high, water solubility may become too high or an organic-inorganic hybrid material (nanocomposite material) may be gelated.
• the functional groups may form salts with cations such as alkali metal ions (for example, Na + , K + , or the like) or ammonium ions .
• the number average molecular weight of the block copolymer is preferably 1000 to 100000, more preferably 2000 to 80000, and especially preferably 3000 to 50000.
• the block copolymer with the number average molecular weight of at least 1000 forms a stable dispersion.
• the block copolymer with the number average molecular weight of at most 100000 increases organic solvent solubility.
• a refractive index of the block copolymer used in the present invention is preferably 1.50 or more, more preferably 1.55 or more, furthermore preferably 1.60 or more, and especially preferably 1.65 or more.
• the refractive index used herein is measured using Abbe's refractometer (a product of Atago, model: DR-M4 ) with incident light of 589 nm wavelength.
• a glass transition temperature of the block copolymer used in the present invention is preferably in a range of 80 0 C to 400 0 C, and more preferably 130 0 C to 380 0 C.
• the block copolymer with the glass transition temperature of at least 80 0 C increases heat resistance.
• the block copolymer with the glass transition temperature of at most 400 0 C improves processability .
• the block copolymer used in the invention has optical transmittance of at least 80% measured at the wavelength of 589 nm with the thickness of 1 mm. It is more preferable that the optical transmittance is at least 85%.
• Specific examples of the block copolymers (illustrated compounds of Pl to P20) are listed in the following. However, the block copolymers used in the present invention are not limited following specific examples. [Table 1]
• the block copolymer is synthesized utilizing living radical polymerization and living ion polymerization, and techniques to protect carboxyl group or introduce a functional group to a polymer as necessary. It is also possible to synthesize the block copolymer by radical polymerization of polymers having terminal functional groups, and formation of bonds between polymers having terminal functional groups. In particular, it is preferable to utilize living radical polymerization and living ion polymerization in view of molecular weight control and yield of block copolymer. Production methods of the block copolymer are described in, for example, "Synthesis and reaction of polymer (1)" edited by The Society of Polymer Science, Japan, and published by Kyoritsu Shuppan, Co., Ltd.
• the inorganic fine particles (inorganic nanoparticles) used in the present invention include, for example, oxide fine particles and sulfide fine particles, more specifically, zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles, tin oxide fine particles, and zinc sulfide fine particles.
• the inorganic fine particles are not limited to those. Of those, metal oxide fine particles are especially preferable.
• one selected from the group consists of zirconium oxide fine particles, zinc oxide fine particles, tin oxide fine particles and titanium oxide fine particles is preferable, and one selected from the group consists of zirconium oxide fine particles, zinc oxide fine particles, and titanium oxide fine particles is more preferable. Furthermore, it is especially preferable to use zirconium oxide fine particles with low photocatalytic activity and excellent transparency in the visible light region.
• a dispersion of two or more kinds of the above inorganic fine particles may be used in view of refractive index, transparency, and stability.
• the above inorganic fine particles may be doped with different kinds of elements, and surfaces of the inorganic fine particles may be covered with dissimilar metal oxide such as silica and alumina. It is also possible that the inorganic fine particles are surface-modified with silane coupling agent, titanate coupling agent or the like.
• Production methods of inorganic fine particles used in the present invention are not particularly limited, and any well-known method can be used.
• desired fine oxide particles are produced using metal halide or metal alkoxide as a raw material, and hydrolyzing the raw material in a reaction system containing water.
• zirconium oxide fine particles and its suspension following methods to prepare zirconium oxide fine particles and its suspension are known, and any of them may be used: a method to prepare zirconium oxide suspension in which a solution containing zirconium salt is neutralized by an alkali to obtain zirconium hydrate, and the obtained zirconium hydrate is dried and sintered and then dispersed in a solvent; a method to prepare zirconium oxide suspension in which a solution containing zirconium salt is hydrolyzed; a method in which zirconium oxide suspension is prepared by hydrolysis of a solution containing zirconium salt and then the prepared zirconium oxide suspension is ultrafiltered to obtain zirconium oxide; a method to prepare zirconium oxide suspension by hydrolysis of zirconium alkoxide; and a method to prepare zirconium oxide suspension by heating and applying pressure to a solution containing zirconium salt under hydrothermal condition.
• Titanyl sulfate is exemplified as a raw material for the synthesis of titanium oxide fine particles.
• Zinc salts such as zinc acetate and zinc nitrate are exemplified as raw materials for the synthesis of zinc oxide fine particles.
• Metal alkoxides such as tetraethoxysilane and titanium tetraisopropoxide are also suitable for raw materials of inorganic fine particles.
• the synthetic methods of such inorganic fine particles include, for example, a method described in pages 4603 to 4608 of Japanese Journal of Applied Physics, vol. 37 (1998), and pages 241 to 246 of Langmuir, vol. 16, issue 1 (2000).
• oxide fine particles are synthesized by a sol formation method
• a procedure of forming a precursor such as a hydroxide and then dehydrocondensing or peptizing the same with an acid or an alkali, and thereby forming a hydrosol, as in the synthesis of titanium oxide fine particles using titanyl sulfate as a raw material.
• the precursor is isolated and purified by any known method such as filtration and centrifugal separation in view of purity of a final product.
• the sol particles in the obtained hydrosol may be insolubilized in water and isolated by adding an appropriate surfactant such as sodium dodecylbenzene sulfonate (abbreviated DBS) or dialkylsulfosuccinate monosodium salt (a product of Sanyo Chemical Industries, Ltd., trade name "ELEMINOL JS-2”) to the hydrosol.
• DBS sodium dodecylbenzene sulfonate
• ELEMINOL JS-2 dialkylsulfosuccinate monosodium salt
• thermoplastic polymer used in the present invention may be dissolved in the organic solvent.
• Examples of the solvent used in the above-mentioned methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone and anisole.
• One kind or a mixture of two or more kinds of the solvents may be used.
• the lower limit of the number average particle size of the inorganic fine particles used in the present invention is preferably at least 1 nm, more preferably at least 2 nm, and furthermore preferably at least 3 nm, and the upper limit thereof is preferably at most 15 nm, more preferably at most 10 nm, and furthermore preferably at most 7 nm.
• the number average particle size of the inorganic fine particles used in the present invention is preferably from 1 nm to 15 nm, more preferably 2 nm to 10 nm and furthermore preferably from 3 nm to 7 nm.
• the "number average particle size" used herein is measured using, for example, an X ray diffraction (XRD) device or a transmission electron microscope (TEM) .
• a refractive index of the inorganic fine particles used in the present invention is preferably in a range of 1.9 to 3.0 at the wavelength of 589 nm at 22 0 C, and more preferably in a range of 2.0 to 2.7, and especially preferably in a range of 2.1 to 2.5.
• the refractive index of the inorganic fine particles is at most 3.0, Rayleigh scattering is suppressed since a difference in refractive indices between the inorganic fine particles and the thermoplastic polymer is not so large.
• the refractive index of the inorganic fine particles is at least 1.9, a produced optical lens achieves a high refractive index.
• the refractive index of the inorganic fine particles is obtained by, for example, measuring the refractive index of a transparent film made of an organic-inorganic hybrid material containing the inorganic fine particles and the thermoplastic polymer used in the present invention with Abbe' s refractometer (for example, a product of Atago, model: DM-M4), and converting the measured value using a refractive index of the thermoplastic polymer component separately measured. It is also possible to calculate the refractive index of the inorganic fine particles by measuring refractive indices of inorganic fine particle dispersions having different concentrations.
• Abbe' s refractometer for example, a product of Atago, model: DM-M4
• the content of inorganic fine particles in an organic-inorganic hybrid material of the present invention is preferably 20 mass% to 95 mass%, and more preferably 25 mass% to 70 mass%, and especially preferably 30 mass% to 60 mass% in view of transparency and achieving a high refractive index.
• a mass ratio between the inorganic fine particles and thermoplastic polymer (dispersion polymer) is preferably 1:0.01 to 1:100, and more preferably 1:0.05 to 1:10, and especially preferably 1 : 0.05 to 1 : 5 in view of dispersibility .
• nanocomposite material contains inorganic fine particles and thermoplastic polymer having a functional group, in at least a main chain end and a side chain, capable of forming any kind of chemical bond with the inorganic fine particles.
• Such nanocomposite material is effectively utilized as a raw material for an optical lens, and injection molded or press molded using a mold having a spherical or nonspherical surface.
• the combined use of the produced optical lens, a plastic lens, and a glass lens is effective as an optical component for various optical-system units.
• the optical-system unit including the optical lens made of the above-described nanocomposite material is described in the following. Note that each embodiment is the optical system unit used as a taking optical system 2 of a digital camera incorporated in a mobile phone as shown in Fig. 2.
• An optical system unit shown in Fig. 3 is constituted of an aperture stop 4 disposed on an image side, a lens unit that is composed of first lens 5 and second lens 6 and disposed behind the aperture stop 4, and a plane parallel plate 7.
• the first lens 5 is a plastic lens made of, for example, methacrylate, and both surfaces thereof are aspheric.
• the second lens 6 is a plastic lens of positive refractive power to which the present invention is applied, and both surfaces thereof are aspheric.
• the parallel plate 7 is a cover plate for protecting a photoelectric surface of an imaging element of a CCD image sensor and the like, and is made of an optical glass such as BK7. Lens data of this optical system unit is shown in the following table. The data show values when the aspheric surface is represented by the following formula:
• Z [ (Y 2 /R) / ⁇ 1+V(1-K(Y 2 /R 2 ) ) H+ ⁇ AiY 1
• Z is a length of a normal line extended from a point A to a point B on the aspheric surface, in which the point A is distant from an optical axis by Y and the point B is a contact plane (plane perpendicular to the optical axis) of the aspheric surface vertex;
• Y is the distance from the optical axis
• R is a curvature radius of the aspheric surface near the optical axis
• the focal distance f is 3.77 mm
• the F number is 4.0
• the angle of field 2 ⁇ is 63.6°.
• the spherical aberration, the astigmatism and the distortion are as shown in Fig. 4.
• the thickness of the second lens 6 can be about 1.2 mm. Therefore, the whole article can be downsized.
• surfaces of each lens 5 and 6 are made aspheric. Owing to this, the aberration of each lens 5 and 6 is well reduced, as shown in Fig . 4 .
• An optical system unit shown in Fig. 5 is constituted of the aperture stop 4 disposed on the image side, a lens unit that is composed of first lens 10, second lens 11 and third lens 12 and disposed behind the aperture stop 4, and the parallel plate 7.
• the first and third lenses 10 and 12 are plastic lenses made of, for example, methacrylate, and both surfaces thereof are respectively aspheric.
• the second lens 11 is a negative plastic lens made of the nanocomposite material of the present invention, and both surfaces thereof are aspheric.
• Lens data of the optical system unit shown in Fig. 5 is shown in the following table. Note that the focal distance f is 4.80 mm, the F number is 3.62, and the angle of field 2 ⁇ is 68.6°.
• the spherical aberration, the astigmatism and the distortion are as shown in Fig. 6.
• An optical system unit shown in Fig. 7 is constituted of the aperture stop 4 disposed on the image side, a lens unit that is composed of first lens 15, second lens 16, third lens 17 and fourth lens 18 and disposed behind the aperture stop 4, and the parallel plate 7.
• the first lens 15 is a plastic lens made of plastic material "ZEONEX 330R" (trade name) manufactured by ZEON corporation, and both surfaces thereof are aspheric.
• the second lens 16 is a negative plastic lens made of the nanocomposite material of the present invention, and both surfaces thereof are aspheric.
• the third and fourth lenses 17 and 18 are plastic lenses made of plastic material "ZEONEX E48R" (trade name) manufactured by ZEON corporation, and both surfaces thereof are respectively aspheric. Lens data of the optical system unit shown in Fig.
• the focal distance f is 5.87 mm
• the F number is 2.82
• the angle of field 2 ⁇ is 62.4°.
• the spherical aberration, the astigmatism and the distortion are as shown in Fig. 8.
• the second lens 6 of the first embodiment, the second lens the second embodiment, and the second lens 16 of the third embodiment are respectively made of the nanocomposite material of the present invention and have the refractive index of 1.654 and the abbe's number of 28.8.
• the nanocomposite material exhibiting such optical properties can be refined according to the following method.
• N, N' -dimethylacetamide is added to 500 g of the hydrous zirconium suspension liquid (concentration: 15% by mass) prepared in (1) above, and the resulting mixture is concentrated to the amount of about 500 g or less under reduced pressure, followed by solvent substitution.
• N, N' -dimethylacetamide is added to adjust a concentration, thereby obtaining 15% by mass zirconium oxide dimethylacetamide dispersion liquid.
• a mixture of 2.1 g of tert-butylacrylate, 0.72 g of 2-bromo-2-methylpropionic acid tert-butyl ester, 0.46 g of cropper bromide (I), 0.56 g of N, N, N' , N' ,N" , N" -pentamethyldiethylene tetramine, and 9 ml of methyl ethyl ketone is prepared, and air in the mixture is substituted by nitrogen.
• the mixture is agitated in an oil bath at a bath temperature of 80°C for 1 hour, and 136.2 g of styrene is added thereto under a nitrogen gas stream.
• the mixture is agitated in an oil bath at a bath temperature of 90 0 C for 16 hours and cooled to room temperature. Then, 100 ml of ethyl acetate and 30 g of alumina are added to the mixture and agitated for 30 minutes. This reaction liquid is filtered and a filtrate is delivered by drops into excess methanol. The formed precipitation is washed with methanol and dried. Thereby, 61 g of polymer is obtained. This polymer is dissolved in 300 ml of toluene, and 6 g of p-toluenesulfonic acid-hydrate is added thereto and refluxed by heating for 3 hours. This reaction liquid is delivered by drops into excess methanol.
• this polymer has the number average molecular weight of 32000 and the weight average molecular weight of 35000.
• the refractive index of this polymer measured by the Abbe's refractometer is 1.59.
• Thermoplastic polymer P-I, m-terphenyl and surface finishing agent ( ⁇ -naphthylacetic acid) are added to the zirconium oxide dimethylacetamide dispersion liquid such that the weight ratio of ZrO2 solid content/P-1/m-terphenyl/ ⁇ -naphthylacetic acid becomes 41.7/45.8/4.2/8.3, and uniformly mixed by agitation.
• the dimethylacetamide solution is concentrated by heating under reduced pressure.
• the concentrated residue is thermally compressed by a mold whose surface is made of SUS (temperature: 180 0 C, pressure: 13.7 MPa, time: 2 minutes) . Thereby, the molded product with a thickness of 1 mm (lens base material) is obtained.
• the optical lens according to the present invention is used as a lens having highest refractive index among the lenses constituting the optical system unit. Since the conventional plastic lenses with low refractive indices can be used for other lenses, production cost of the optical system unit can be reduced.
• the cover plate for protecting the photoelectric surface of each imaging element is a glass lens with no optical (refractive) power.
• the optical lens made of nanocomposite material of the present invention can be combined with glass lenses with, for example, positive or negative power (both spherical and aspheric lenses are applicable) .
• the nanocomposite material of the present invention has higher refractive index and higher dispersion as compared to the conventional plastic materials for the optical lenses.
• the nanocomposite material of the present invention is used for positive or negative lens with low optical power so that the chromatic aberration and curvature of field are reduced.
• the following conditional equation is preferably satisfied: 4 x f > f p where "f p " is the focal distance of the optical lens and "f" is the focal distance of the whole system including this optical lens.
• the usage of the nanocomposite material of the present invention reduces variation in refractive index due to the environmental temperature change to practically ignorable level. Therefore, when the optical lens of the present invention is used as a lens disposed where temperatures vary most widely among the plastic lenses constituting various optical system unit, the temperature properties of the article is improved.
• optical system units described in the above embodiments are used as the taking optical system of the digital camera incorporated in the mobile phone, the optical system units according to the present invention are applicable in other purposes as well.
• the optical system units of the present invention can be applied to an image projection device in which a liquid crystal panel is used as an image display device, when the lenses are designed to satisfy necessary optical conditions.
• the optical system units of the present invention can also be applied to an optical system of various optical devices such as optical measuring device for interferometer/optical ranging device.

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• Optics & Photonics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Lenses (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 2007
  • 2007-08-17 JP JP2007212781A patent/JP2009047836A/ja active Pending
• 2008
  • 2008-08-13 WO PCT/JP2008/064765 patent/WO2009025275A1/en active Application Filing
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