TW200914254A

TW200914254A - Optical lens, optical system unit and optical device

Info

Publication number: TW200914254A
Application number: TW97130973A
Authority: TW
Inventors: Kenichi Sato; Tatsuhiko Obayashi; Seiichi Watanabe
Original assignee: Fujifilm Corp
Priority date: 2007-08-17
Filing date: 2008-08-14
Publication date: 2009-04-01
Also published as: WO2009025275A1; JP2009047836A

Abstract

A taking optical system of a digital camera is constituted of an aperture stop (4), a first lens (5), a second lens (6) and a plane parallel plate (7). The first lens (5) is composed of a plastic lens formed of a conventional plastic material, and has a refractive index of 1. 510. The second lens (6) is an optical lens made of a nanocomposite material formed by mixing inorganic fine particles into a thermoplastic polymer having a functional group, bind chemically to the inorganic fine particles, in at least one of a main chain end and a side chain, and has a refractive index of 1.654. The parallel plate (7) is composed of a glass having a refractive index of 1.516. Even when the second lens (6) is the plastic lens, the taking optical system can be made compact and achieves sufficient refractive index without deteriorating the transmittance properties thereof.

Description

200914254 九、發明說明：【發明所屬之技術領域】本發明關於一種由熱塑性聚合物製成之光學透鏡，/ 種包括所述光學透鏡之光學系統單元，以及一種使用戶斤述光學系統單元之光學元件。【先前技術】200914254 IX. Description of the Invention: [Technical Field] The present invention relates to an optical lens made of a thermoplastic polymer, an optical system unit including the optical lens, and an optical device for allowing a user to recite an optical system unit element. [Prior Art]

由諸如丙烯酸樹脂或之透明塑膠材料形成之光學透鏡驗絲元件巾。錢，與絲麵相比，可用於製造光學透鏡之習知轉材料具有諸如以下缺陷：，射率（refractive index)不能增加至較高值且焦距（f〇cal 1哪仇）根據隨溫度變化之折射率的變化而改變。為克服 ^^缺1^ ’研九將奈米1及無機細粒(in〇rganicfmeParticles) ς ^於塑膠基質中之各種奈米複合材料（有機·無機混合材枓）的使用。 ^於日本專利早期公開第聽也搬號中之奈米料是藉由將最大長度（粒子直徑）為3Q奈米的氧化材散於透明轉基質中來製備。此奈米複合料葬A 不2增加至較高值。'然而’所述奈米複合材塑膠基無機細粒之折射率的增加而抵消述公Η安据〜主物率，因而防止總折射率的改變。上奈米至15奈米之範圍内，以防=學透= 方面為4備具有高折射率之奈米複合材料，已 200914254 知選擇具有高折射率之無機細粒，根據申=; 因而不適用;綱鏡;有低透明度 2+，化===::: 透射率之_果際效用。粒子直徑機細粒不具有實佳為至多嶋。粒子直^更基於上述模擬，為製備用 ^^夕不1。透射率的奈米複人好子边獍之具有優良光學 =:::機較^ =_細_=:;==得學性質。 5材料製成之光學透鏡不能達成所需光【發明内容】繁於上述，本翻之目的在於提供—種二均一折射率分佈以及優良光學性質之光學透f射 t達成高折射率且改良溫度性質，所述光但機細粒分散於塑膠基質中之奈米複合材鏡 200914254 提供-種包括所述光學透鏡之光學系統單元為達成上述目的以及其他目的，由| ;複2料(有機他合材料)來製造本粒均：地it:直徑(取大長度)小於Μ奈米之無機細有塑膠基質中，使用在主鏈末端或側鏈中1 聚少一個無機細粒形成化學鍵之官能基的熱塑性鏈“機rft)。所述官能基與無機細粒鍵結且藉此使主間:留有空間。因此，無機細粒均-地分散:塑光學性質，諸如高光學透射率以及均—==‘，，、貝不優良明之口此Ig光學透鏡是由塑膠製成，但本發 t先學魏可祕具有寬泛溫度變化之場射。另外，用歸透鏡之熱紐特徵，使用具有球形或非球形先具f由射出成形或㈣成形來敎地大規模製造夠:其Γ ’攸而引起低生產成本。亦有可能藉由適當選擇 “Sr無機細粒而使折射率達到至少W。根據本 (諸U光子透鏡或光學系統單元可應用於各種光學元件如成像元件、投影元件、光學量測元件）中。相tf·根ί本發明’與由習知奈米複合材料製成之光學透鏡上述奈米複合材料製成之光學透鏡具有顯著較高 200914254 透明度、均一折射率分佈以及優良光學性質。因為影響折射率調節之無機細粒的尺寸比習知無機細粒小，且所述無機細粒比習知無機細粒更均一地分散於塑膠基質中，所以上述奈米複合材料展現更能夠遵循溫度變化以抑制折射率隨溫度改變之補償效應。【實施方式】 [熱塑性聚合物] 有效地用於製造本發明之光學透鏡之熱塑性聚合物 (熱塑性）在主鏈末端以及側鏈的至少一者中具有能夠與無機細粒形成任何種類之化學鍵的官能基。所述熱塑性聚合物之較佳實例包括： (1)在侧鏈中具有至少一個官能基之熱塑性聚合物，且所述官能基選自以下基團： [化學式1]An optical lens test element towel formed of a transparent plastic material such as acrylic or plastic. Money, compared to silk, conventional materials that can be used to make optical lenses have the following drawbacks: the refractive index cannot be increased to a higher value and the focal length (f〇cal 1) is based on temperature. The change in refractive index changes. In order to overcome the use of various nanocomposites (organic/inorganic hybrid materials) in which nanometer 1 and inorganic fine particles (in〇rganicfmeParticles) are used in a plastic matrix. The nanomaterial in the early publication of the Japanese Patent Publication was prepared by dispersing an oxidized material having a maximum length (particle diameter) of 3 Q nanometers in a transparent transfer substrate. This nanocomposite burial A does not increase to a higher value. 'However' the increase in the refractive index of the plastic-based inorganic fine particles of the nanocomposite cancels the change in the total material refractive index, thereby preventing the change in the total refractive index. From the range of nanometers to 15 nanometers, in case of prevention, the surface of the nanocomposites with high refractive index is 4, and it has been known to select inorganic fine particles with high refractive index according to 200914254, according to Applicable; Gang Mirror; has low transparency 2+, chemistry ===::: Transmittance _ fruit effect. The particle diameter machine fine particles are not as good as at most. The particle is directly based on the above simulation, and is used for the preparation. The transmittance of the nano-recovery has a good optics =::: machine is better than ^ = _ fine _=:; == learning properties. 5 optical lens made of material can not achieve the required light [Summary of the invention] In the above, the purpose of this is to provide a two-to-one refractive index distribution and excellent optical properties of the optical transmittance to achieve high refractive index and improved temperature The nature of the nano-composite mirror 200914254, which is dispersed in a plastic matrix, provides an optical system unit including the optical lens for achieving the above purpose and other purposes, by | The material is made of the same material: the diameter of it: the diameter (takes a large length) is less than that of the inorganic fine plastic matrix of the nanometer, and the function of forming a chemical bond is formed by using one inorganic fine particle at the end of the main chain or in the side chain. The thermoplastic chain of the base is "machined." The functional group is bonded to the inorganic fine particles and thereby leaving a space between the main compartments. Therefore, the inorganic fine particles are uniformly dispersed: plastic optical properties such as high optical transmittance and Both—==',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Use with ball F having a non-spherical first iv injection molding or shaping to be objective for large scale manufacture: which Γ 'Yau caused by low production costs also may be suitably selected "Sr refractive index of at least the inorganic fine W. According to the present (the U-photon lenses or optical system units can be applied to various optical elements such as imaging elements, projection elements, optical measuring elements). The invention relates to an optical lens made of a conventional nano composite material. The optical lens made of the above nano composite material has a significantly higher transparency, uniform refractive index distribution and excellent optical properties. Since the size of the inorganic fine particles affecting the refractive index adjustment is smaller than that of the conventional inorganic fine particles, and the inorganic fine particles are more uniformly dispersed in the plastic matrix than the conventional inorganic fine particles, the above-mentioned nano composite material exhibits more compliance. Temperature changes to suppress the compensation effect of refractive index change with temperature. [Embodiment] [Thermoplastic polymer] The thermoplastic polymer (thermoplastic) effective for producing the optical lens of the present invention has at least one of a main chain end and a side chain capable of forming any kind of chemical bond with inorganic fine particles. Functional group. Preferred examples of the thermoplastic polymer include: (1) a thermoplastic polymer having at least one functional group in a side chain, and the functional group is selected from the group consisting of: [Chemical Formula 1]

OR 11OR 11

OR 13 P— OR12 —0 — P — OR14 0 0 、[RI1、Rl2、Rl3以及R]4分別可為氫原子、經取代或未餐取代之録、經取代絲經取代之縣、經取代或未經取代之炔基或經取代或未經取代之芳基的任一者]、、-〇S〇3H、_c〇2h 以及，ORl5)m]R]uR]5 以及 ^每-者為A原子、經取代或未經取代之絲、經 =經取狀職、經取代絲峰代之絲或經取 !取代之芳基，且ml為1至3之整數]. 〆 200914254 (2)在主鏈末端之至少一部分中具有至少一個官能基之熱塑性聚合物，且所述官能基選自以下基團： [化學式2] OR21 . OR23 24 p— OR22 〇OR 13 P— OR12 —0 — P — OR14 0 0 , [RI1, Rl2, Rl3, and R]4, respectively, may be a hydrogen atom, a substituted or unsubstituted meal, a substituted silk substituted, a substituted or Any of the unsubstituted alkynyl groups or substituted or unsubstituted aryl groups], , -〇S〇3H, _c〇2h, and ORl5)m]R]uR]5 and ^ per-A An atom, a substituted or unsubstituted filament, a substituted or substituted filament, or a substituted aryl group, and ml is an integer from 1 to 3.] 〆200914254 (2) a thermoplastic polymer having at least one functional group in at least a portion of the end of the main chain, and the functional group is selected from the group consisting of: OR21. OR23 24 p-OR22 〇

CC

[R21、R22、R23以及R24之每-者可為氫原子、經取代或未經取代之烷基、經取代或未經取代之烯基、經取代或未經取代之炔基或經取代或未經取代之芳基的任一者]、 1〇3H、-oso3H、-co2h 以及-Si(〇R25)m2Rt63 m2[R25 以及 R之每一者為氫原子、經取代或未經取代之烷基、經取代或未經取代之烯基、經取代或未經取代之炔基或經取代或未經取代之芳基，且m2為1至3之整數];以及 (3)由疏水性段與親水性段構成之嵌段共聚物。在下文中，詳述熱塑性聚合物（1)至（3)。熱塑性聚合物（1) 本發明中所用之熱塑性聚合物（1 )在側鏈中具有能夠與無機細粒形成化學鍵之官能基。本文中所用之“化學鍵’’包括（例如）共價鍵、離子鍵、配位鍵以及氫鍵。若熱塑性聚合物（1)具有多個官能基，則各官能基可與無機細粒形成不同化學鍵。藉由在將熱塑性聚合物與無機細粒分散於有機溶劑中之後，官能基與無機細粒之間化學鍵的存在來判定官能基是否能夠與無機粒子形成化學鍵。熱塑性聚合物之所有或一部分官能基可與無機細粒形成化學 10 200914254 鍵。能夠與無機細粒形成化學鍵之官能基藉由與無機細粒形成化學鍵而將所返無機細粒穩定地分散於熱塑性聚八物中。所述官能基選自： σ [化學式3][R21, R22, R23 and R24 may each be 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 Any of the unsubstituted aryl groups], 1〇3H, -oso3H, -co2h, and -Si(〇R25)m2Rt63 m2 [R25 and each of R are a hydrogen atom, a substituted or unsubstituted alkane Alkenyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl or substituted or unsubstituted aryl, and m2 is an integer from 1 to 3; and (3) by hydrophobic segment A block copolymer composed of a hydrophilic segment. Hereinafter, the thermoplastic polymers (1) to (3) will be described in detail. Thermoplastic polymer (1) The thermoplastic polymer (1) used in the present invention has a functional group capable of forming a chemical bond with inorganic fine particles in a side chain. As used herein, "chemical bond" includes, for example, a covalent bond, an ionic bond, a coordinate bond, and a hydrogen bond. If the thermoplastic polymer (1) has a plurality of functional groups, each functional group may be different from the inorganic fine particles. A chemical bond determines whether a functional group can form a chemical bond with an inorganic particle by the presence of a chemical bond between the functional group and the inorganic fine particle after dispersing the thermoplastic polymer and the inorganic fine particle in an organic solvent. All or part of the thermoplastic polymer The functional group may form a chemical with the inorganic fine particles 10 200914254. The functional group capable of forming a chemical bond with the inorganic fine particles stably disperses the returned inorganic fine particles in the thermoplastic polystyrene by forming a chemical bond with the inorganic fine particles. The functional group is selected from the group consisting of: σ [Chemical Formula 3]

[R] OR11 OR13 1 12 1 —p — ORu — Ο — p — OR14[R] OR11 OR13 1 12 1 —p — ORu — Ο — p — OR14

II o 、L 母一有1马鼠原子、經取代或未經取代之烷基、經取代或未經取代之烯基、經取代或未經取代之炔基或經取代或未經取代之芳基的任一 -S〇3H、-〇S03H、-C02H 4-Si(〇R】5)m]Ri63_m】[Rl5 以及 r16 之每-者為氫原子、經取代絲雜代之錄、經取代或未經取代之職、經取代或未娜狀絲驗經取代之芳基，且ml為1至3之整數]。八取木㈣1至3(M嶋子，且更佳具有1至2〇，原子，且其實例包括甲基、乙基以及正丙基。經取代燒基包括（例如）关惊芙。关、ρ I y 乂土气子，方方絲車父佳具有7至30個碳原 ΐ 7至2G個碳原子，且其實例包的基以及 =甲氧基卞基。職較佳具有2至3G㈣原子，且更佳具歸臭至二個碳原子’且其實例包括乙烯基以及2_苯基乙 ^=較佳具有2至2Q個碳科，且更佳具有2至反’、子，且其實例包括乙块基以及2_笨基乙炔基。芳 200914254 6至3〇個碳原子，且更佳具有6至2〇個碳原 :’且”貫例包括苯基、2,4,6_三溴苯基以及μ萘基。本文之ϊ基包括雜芳基。烧基、稀基、快基以及芳基之土之戶、例除包括上述燒基、稀基、亦包㈣素料（例如縣絲以及方基外，原子)以及燒氧基(例如===原一 R15以及R16之參社〜1基以及乙乳基）。 Γ: R]1、R12、R13以及土妷原子數、官能基以及取代基與基相同。ml較佳為3。之較佳碳原子數、官能基以及取代在上述官能基中，較佳 [化學式4] 4 'II o , L mother has 1 mad atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl or substituted or unsubstituted aryl Any of the groups -S〇3H, -〇S03H, -C02H 4-Si(〇R]5)m]Ri63_m][Rl5 and r16 are each a hydrogen atom, substituted by a halogen, substituted Or an unsubstituted, substituted or unsubstituted aryl group, and ml is an integer from 1 to 3.八木 (4) 1 to 3 (M 嶋, and more preferably has 1 to 2 〇, an atom, and examples thereof include a methyl group, an ethyl group, and a n-propyl group. The substituted alkyl group includes, for example, Guan Yufu. ρ I y 乂 rustic, the square wire car father has 7 to 30 carbon atoms ΐ 7 to 2G carbon atoms, and its example package base and = methoxy fluorenyl group. The user preferably has 2 to 3G (four) atom And more preferably odorous to two carbon atoms' and examples thereof include a vinyl group and a 2-phenylene group, preferably having 2 to 2Q carbon families, and more preferably having 2 to anti-, sub-, and Examples include an E-block group and a 2-phenylidene ethynyl group. Aromatic 200914254 6 to 3 carbon atoms, and more preferably 6 to 2 carbon atoms: 'and' examples include phenyl, 2, 4, 6_ Tribromophenyl and umnaphthyl. The fluorenyl group herein includes a heteroaryl group. The base of the alkyl group, the dilute group, the fast group and the aryl group includes, in addition to the above-mentioned alkyl group, the dilute group, and the (four) element material ( For example, the county wire and the square base, the atom and the alkoxy group (for example, === the original R15 and the R16 and the 1st base and the ethyl lactate). Γ: R]1, R12, R13 and the number of earthworms , functional groups and Group is preferably the group .ml same number of carbon atoms is preferably 3, the functional groups and substituents in the above functional groups, preferably [Chemical Formula 4] 4 '

OR11 I —P — OR 12OR11 I —P — OR 12

OR 13OR 13

〇 OR 14 0 ii 、〇 -S03H、-C〇2H 或_ 、 [化學式5] )mlR 3-ml。更佳官能基為 OR]1 —P —〇RJII 〇 ,11 ,12〇 OR 14 0 ii , 〇 -S03H, -C〇2H or _, [Chemical Formula 5] ) mlR 3-ml. More preferred functional groups are OR]1 —P —〇RJII 〇 ,11 ,12

OR 13 14 或-c〇2H。尤其較佳之官能基為： 12 200914254 [化學式6] OR11I —P — OR12I! 〇 OR13I 〇 -— P — OR14 II o 本毛明中所用之熱塑性聚合物尤其較佳為OR 13 14 or -c〇2H. Particularly preferred functional groups are: 12 200914254 [Chemical Formula 6] OR11I - P - OR12I! 〇 OR13I 〇 - - P - OR14 II o The thermoplastic polymer used in the present invention is particularly preferably

通式⑴表枕單元之絲物。所述料物是藉= 文通式（2)表不之乙烯基單體的共聚而人通式（1) ° [化學式7]The filament of the formula (1) pillow unit. The material is a copolymer of a vinyl monomer represented by the formula (2) and a formula (1) ° [Chemical Formula 7]

RR

I 4CH—C 如I 4CH—C as

II

X一（ Y )q— Z 通式（2)X-(Y)q- Z general formula (2)

[化學式8] R[Chemical Formula 8] R

X— ( Y )q— Z 表示氯原子、鹵素表示由-C〇2-、-OCO-、 '〇-、-s-、_nh-以及經取族群中選出之二價鍵聯基在通式（1 )以及（2)中，原子以及甲基之一者。‘‘ X，’ CONH-、-OCONH…〇c〇〇·、代或未經取代之伸芳基所構成的 13 200914254 團。“x”更佳為-co2-或對伸苯基。 “Y”表示具有1至30個碳原子之二價鍵聯基團。碳原子數較佳為1至20，更佳為2至10，且進一步較佳為2 至5。更詳細而言，可使用伸院基、伸院基氧基、伸院基氧羰基、伸芳基、伸芳基氧基、伸芳基氧羰基以及上述基 .團之組合。詳言之，較佳為伸烷基。 “q”表示0至18之整數。“q”更佳為0至10之整數。“q”進一步較佳為0至5之整數。“q”尤其較佳為 f % ; 0 或 1。 “Z”表示由下列基團所構成的族群中選出之官能基： [化學式9] OR11 j OR13 | —P — OR12 II 1 —〇—p —〇 R14 [I II 0 、 II 〇 -S03H、-0S03H、-C02H 以及-Si(OR15)mlR163.ml。較佳官能基為： [化學式10] OR11 OR13X—( Y )q— Z represents a chlorine atom, and halogen represents a divalent bond selected from —C〇2-, —OCO—, '〇-, —s-, _nh-, and selected from the group. (1) and (2), one of an atom and a methyl group. ‘‘X,’ CONH-, -OCONH...〇c〇〇·, or unsubstituted aryl group 13 200914254. More preferably, "x" is -co2- or p-phenyl. "Y" represents a divalent linking group having 1 to 30 carbon atoms. The number of carbon atoms is preferably from 1 to 20, more preferably from 2 to 10, and still more preferably from 2 to 5. More specifically, a combination of a stretching base, a stretching base oxygen group, a stretching oxycarbonyl group, an exoaryl group, an aryloxy group, an aryloxycarbonyl group, and the above group may be used. In particular, an alkyl group is preferred. "q" represents an integer from 0 to 18. "q" is more preferably an integer from 0 to 10. "q" is further preferably an integer of 0 to 5. "q" is particularly preferably f%; 0 or 1. "Z" represents a functional group selected from the group consisting of: [Chemical Formula 9] OR11 j OR13 | —P — OR12 II 1 —〇—p —〇R14 [I II 0 , II 〇-S03H,- 0S03H, -C02H, and -Si(OR15) mlR163.ml. The preferred functional groups are: [Chemical Formula 10] OR11 OR13

I 1? I —p — OR1 — 0 — p — OR14I 1? I —p — OR1 — 0 — p — OR14

II II 0 、 0 。 14 200914254 c 更佳官能基為：[化學式1】]II II 0, 0. 14 200914254 c The better functional group is: [Chemical Formula 1]]

OR 13 —0 — P — 〇R14IIο ο在本文申，除R]3、、ρ]3 ^一去R 、R 、R15以及R]6之每 π , ^ 'R > ϊ?34> ΐ??5> Ώ ^ CJ 下R以及⑴之^義以及較實例在下文中，描述由通式⑵表示之單然而’可㈣本發财之單體並不限於鱗實例。 [化學式12] A— 1OR 13 —0 — P — 〇R14IIο ο In this paper, except for R]3, ρ]3 ^, and R, R, R15, and R]6, each π, ^ 'R > ϊ?34> ΐ? ?5> Ώ ^ CJ, R, and (1), and comparative examples, hereinafter, the ones represented by the general formula (2) are described, however, the monomers of the present invention are not limited to the scale examples. [Chemical Formula 12] A-1

〇〇〇〇

fP〇 (OH) (q = 5與q = 6之混合物） Α~2 =/.0 T 0 (q = 4與q = 5之混合物）fP〇 (OH) (q = 5 and q = 6 mixture) Α~2 =/.0 T 0 (q = 4 and q = 5 mixture)

_〇十 PO (〇H) 15 200914254 __________c A-3_〇十 PO (〇H) 15 200914254 __________c A-3

PO (OH)PO (OH)

A-5A-5

PO (〇H)2 [化學式13] A-6 =^NH 〇PO (〇H) 2 [Chemical Formula 13] A-6 =^NH 〇

ch2so3h 0 A-8Ch2so3h 0 A-8

IIII

P — OHP — OH

II

OH A-9 (OCH3)3 16 0 200914254 可與由上文通式（2)表示之單體共聚之其他種類的單體描述於”Polymer Handbook 第 2 版”彳 Bmndmp, Wiley Interscienece (1975年)之第2章中第“幻頁中。 • “特疋S之’例如’可列舉選自苯乙烯衍生物、1_乙烯基，、2-乙嫦基萘、乙稀基十坐、丙稀酸、甲基丙稀酸、 • @烯酸Sl、甲基丙稀酸_、丙騎胺、甲基丙稀醯胺、稀 =基化合物、乙稀細、乙稀g旨、衣康酸二垸g旨以及反丁稀一自^之一燒知或單虎酯之具有一個可加成聚合的不飽和鍵之化合物。苯乙烯衍生物之實例包括苯乙烯、2,4,6-三溴苯乙烯、 2-笨基苯乙烯。丙烯酸醋之實例包括丙烯酸曱酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、丙烯酸第三丁酯、丙烯酸氯乙酯、丙婦酸2-經基乙酯、三羥曱基丙烷單丙烯酸酯、丙烯酸苄醋、丙烯酸甲氧基苄酯、丙烯酸呋喃甲酯以及丙烯酸四氫呋喃曱酯。 I’ 曱基丙烯酸酯之實例包括曱基丙烯酸甲酯、曱基丙烯 •酸乙酉旨、甲基丙烯酸丙酯、甲基丙烯酸丁酯、曱基丙烯酸 -第二丁醋、曱基丙烯酸氯乙酯、曱基丙烯酸2_羥基乙酯、三經曱基丙烷單曱基丙烯酸酯、曱基丙烯酸苄酯、曱基丙烯酸甲氧基苄酯、曱基丙烯酸呋喃曱酯以及曱基丙烯酸四鼠°夫喃曱酯。丙烯醯胺之實例包括丙烯醯胺、N-烷基丙烯醯胺（其中烷基具有1至3個碳原子，諸如曱基、乙基或丙基）、 17 200914254 N，N-二烷基丙烯醯胺（其中烷基具有1至6個碳原子）、 N-羥基乙基-N-曱基丙烯醯胺以及N-2-乙醯胺乙基-N-乙醯基丙稀醯胺。甲基丙烯醯胺之實例包括甲基丙烯醯胺、N-烷基曱基 ' 丙烯醯胺（其中烷基具有1至3個碳原子，諸如曱基、乙 • 基或丙基）、N，N-二烧基甲基丙稀酸胺（其中烧基具有1 至6個碳原子）、N-羥基乙基-N-甲基曱基丙烯醯胺以及 N-2-乙醯胺乙基-N-乙醯基曱基丙烯醯胺。稀丙基化合物之實例包括烯丙醋（例如，乙酸烯丙酯、己酸稀丙S旨、辛酸稀丙i旨、月桂酸烯丙醋、棕櫚酸烯丙醋、硬脂酸烯丙酯、苯曱酸烯丙酯、乙醯乙酸烯丙酯以及乳酸烯丙酯）以及烯丙基氧基乙醇。乙稀基鍵之實例包括烧基乙稀基鍵（其中烧基具有1 至10個碳原子），諸如己基乙烯基醚、辛基乙烯基醚、癸基乙稀基驗、乙基己基乙婦基驗、曱氧基乙基乙稀基鍵、乙氧基乙基乙烯基醚、氯乙基乙烯基醚、1-甲基-2,2-二曱 1 - 基丙基乙烯基醚、2-乙基丁基乙烯基醚、羥基乙基乙烯基 - 醚、二乙二醇乙烯基醚、二甲基胺基乙基乙烯基醚、二乙基胺基乙基乙烯基醚、丁基胺基乙基乙烯基醚、苄基乙烯基鍵以及四鼠σ夫喃曱基乙細基驗。乙烯酯之實例包括丁酸乙烯酯、異丁酸乙烯酯、三曱基乙酸乙烯酯、二乙基乙酸乙烯酯、特戊酸乙烯酯、己酸乙烯酯、氯乙酸乙烯酯、二氯乙酸乙烯酯、曱氧基乙酸乙烯酯、丁氧基乙酸乙烯酯、乳酸乙烯酯、丁酸乙烯基-β- 18 200914254 笨酉曰二已基曱S楚乙稀1旨。 ^fit二燒_之實例包括衣康酸二甲醋、衣康酸二乙酉曰以及衣康酴一勺枯、丁酯。反丁烯二酸之二烷酯或單烷酯之實例夂丁烯二酸二丁酯。 ^夕卜，亦可例示丁烯酸、衣康酸、丙烯腈、甲基丙烯腈、順丁烯二.及其類似物。本發明中戶斤田 ^ππ ΛΛΛ 厅用之熱塑性聚合物（1)具有較佳1,000至 jUU,UUU ' ψ j± 〇 ^ ιηΛΛΛΛ 土 3,00〇至 300,000 且尤其較佳 10,000 至 100,000之數量平曰 .,Λ τ 分于虿（number average molecular :二:=1::聚福^ $ /丨、1 、、、土生聚合物（1)之加工性改良，且若其為至川00，則機械強度增加。土从^文^所用之“數量平均分子量，，為基於使用四氫呋 '、、，/奋劑藉由具有 TSK gel GMHxL、TSK gel G4000HXL '及 K gel G2000HxL (Tosoh Corporation 的商標名）管柱之GPC分析儀之差示折射計進行偵測的聚苯乙烯等效分子量。在本發明中所用之熱塑性聚合物（1)中，每個主鏈中 f無機細粒鍵結之官能基之平均數目較佳為0.1至20，更 k為0.5至1〇，且尤其較佳為i至5。若每個主鏈中官能基之平均數目為至多2Q ’則防止由熱塑性聚合物⑴與夕们，、，、梅'，、田粒配位造成之膠凝以及溶液狀態中之黏度增加。若每個主鏈中官能基之平均數目為至少Q1，則無機細粒穩定分散。 200914254 本發明中所用之熱塑性聚合物⑴q (glass transition temperature)車交佳為 8〇至 ’孤又佳為13〇。(：至38(TC。由玻璃轉移温度為至至少，士更物製造具有充分耐熱性之光學元件。葬 L之聚合度為M WC之聚合物，«合物二^性用^^移溫右熱塑性聚合物⑴之折射率與無 1 間存在顯著差異，則有可“料 ^之折射率之 scatt，）。g此，待分散於熱塑性聚合^，細粒之量需要降低以保持模製產之热機合物（1)之折射率為极明度。若熱塑性聚準上之透明椟製在㈣水中所用之_ ”合物⑴’n射率’本發明且更佳為至少U8。此等折射率2^^佳為至少i.55, 長下加以量測。 2 C下在589奈米波 C, $ ( 1 )在589奈米波長下帆、更佳至少之較例描:之熱_合物⑴ 限於下列實例。本發种之_性聚合物並不 20 200914254 [化學式14]OH A-9 (OCH3)3 16 0 200914254 Other kinds of monomers copolymerizable with the monomer represented by the above formula (2) are described in "Polymer Handbook 2nd Edition" 彳Bmndmp, Wiley Interscienece (1975) In Chapter 2, “The Magic Page. • “Special S', for example, may be selected from the group consisting of styrene derivatives, 1-vinylidene, 2-ethenylnaphthalene, ethylidene, and acrylic acid. , methacrylic acid, • olefinic acid Sl, methyl acrylic acid _, propylamine, methyl acrylamide, dilute base compound, ethylene thin, ethylene glucosyl, itaconic acid diterpenoid And a compound having an addition-polymerizable unsaturated bond. Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, 2-phenylstyrene. Examples of acrylic vinegar include decyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-ethyl propyl acrylate, trihydroxy hydrazine propane mono acrylate Ester, benzyl acrylate, methoxybenzyl acrylate, furan methyl acrylate and tetrahydrofuran acrylate. Examples of I'-based methacrylate include methyl methacrylate, decyl propylene acrylate, propyl methacrylate, butyl methacrylate, methacrylic acid-second butyl vinegar, chloroethyl methacrylate 2, hydroxyethyl methacrylate, trimethyl decyl propane monodecyl acrylate, benzyl methacrylate, methoxybenzyl methacrylate, furfuryl decyl acrylate and methacrylic acid Carbamate. Examples of the acrylamide include acrylamide, N-alkyl acrylamide (wherein the alkyl group has 1 to 3 carbon atoms such as an anthracenyl group, an ethyl group or a propyl group), and 17 200914254 N,N-dialkyl propylene. Guanidine (wherein the alkyl group has 1 to 6 carbon atoms), N-hydroxyethyl-N-mercaptopropenylamine and N-2-acetamidoethyl-N-ethylmercaptopropylamine. Examples of the methacrylamide include methacrylamide, N-alkylindenyl 'acrylamide (wherein the alkyl group has 1 to 3 carbon atoms such as an anthracenyl group, an ethyl group or a propyl group), N, N-dialkyl methacrylic acid amine (wherein the alkyl group has 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmercapto acrylamide and N-2-acetamidoethyl- N-Ethyl mercapto acrylamide. Examples of the dipropyl compound include allyl vinegar (for example, allyl acetate, hexanoic acid, octanoic acid, lauric acid, acrylic acid, allyl succinate, allyl stearate, Allyl benzoate, allyl acetate, and allyl lactate) and allyloxyethanol. Examples of the ethylenic bond include a thiol bond (wherein the alkyl group has 1 to 10 carbon atoms), such as hexyl vinyl ether, octyl vinyl ether, thioglycol, ethylhexyl Basic test, oxiranyl ethyl thiol bond, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-diindenyl 1-propyl vinyl ether, 2 -ethylbutyl vinyl ether, hydroxyethyl vinyl-ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylamine Base ethyl vinyl ether, benzyl vinyl bond and four mouse sigma fluorenyl group. Examples of vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl tridecyl acetate, diethyl vinyl acetate, vinyl pivalate, vinyl hexanoate, vinyl chloroacetate, ethylene dichloroacetate Ester, decyloxyvinyl acetate, butoxy vinyl acetate, vinyl lactate, vinyl butyrate-β- 18 200914254 Awkward two has been based on S. Examples of ^fit two-burning _ include acetoic acid dimethyl vinegar, itaconic acid diethyl hydrazine, and a spoonful of dry and butyl esters. An example of a dialkyl or fumarate of maleic acid, dibutyl phthalate. Further, butenoic acid, itaconic acid, acrylonitrile, methacrylonitrile, butylene, and the like can also be exemplified. In the present invention, the thermoplastic polymer (1) used in the field is preferably 1,000 to jUU, UUU ' ψ j ± 〇 ^ ιη ΛΛΛΛ 3,00 〇 to 300,000 and particularly preferably 10,000 to 100,000.曰., Λ τ is divided into 虿 (number average molecular: two: = 1:: Jufu ^ $ / 丨, 1, 、,, the biopolymer (1) process improvement, and if it is tochuan 00, then The mechanical strength is increased. The "quantitative average molecular weight" used by the soil is based on the use of tetrahydrofuran, /, / by TSK gel GMHxL, TSK gel G4000HXL ' and K gel G2000HxL (trademark of Tosoh Corporation) The polystyrene equivalent molecular weight detected by the differential refractometer of the GPC analyzer of the column. In the thermoplastic polymer (1) used in the present invention, the inorganic fine particle bonded in each main chain The average number of functional groups is preferably from 0.1 to 20, more k is from 0.5 to 1 Torr, and particularly preferably from i to 5. If the average number of functional groups in each main chain is at most 2Q', prevention by thermoplastic polymer (1) Gelation and solution state caused by coordination with Xi,,,, plum, The viscosity is increased. If the average number of functional groups in each main chain is at least Q1, the inorganic fine particles are stably dispersed. 200914254 The thermoplastic polymer (1)q (glass transition temperature) used in the present invention is 8〇 to ' Lonely and good is 13 〇. (: to 38 (TC. From the glass transfer temperature to at least, the fabric is made of optical components with sufficient heat resistance. The polymerization degree of the burial L is M WC polymer, «Compound II ^There is a significant difference between the refractive index of the right thermoplastic polymer (1) and the absence of one, and there is a "satt" of the refractive index of the material, which is to be dispersed in the thermoplastic polymer, fine particles. The amount needs to be lowered to maintain the refractive index of the molded thermothermal compound (1) as extremely bright. If the thermoplastic polyimide is transparently tanned in (4) water, the compound (1) 'n-rate' is used in the present invention. More preferably at least U8. These refractive indices are preferably at least i.55, measured in length. 2 C under 589 nm wave C, $ (1) at 589 nm wavelength, better At least the description of the heat: the compound (1) is limited to the following examples. The _ polymer of the present invention is not 20 2009 14254 [Chemical Formula 14]

1 I B1 I B

Η cΗ c

PO(OH)2 (q = 4與q = 5之混合物）PO(OH)2 (a mixture of q = 4 and q = 5)

(q = 4與q = 5之混合物）(q = 4 and q = 5 mixture)

PO(OH) 21 200914254 A· ^ 丄I J-/XO. · [化學式151 B__4 CH3toCH3PO(OH) 21 200914254 A· ^ 丄I J-/XO. · [Chemical Formula 151 B__4 CH3toCH3

r (q = 5與q = 6之混合物） B-5 CH;r (a mixture of q = 5 and q = 6) B-5 CH;

(q = 5與q = 6之混合物） B —(q = 5 and q = 6 mixture) B —

PO(OH)2 22 200914254PO(OH)2 22 200914254

Ο I po(oh)2Ο I po(oh)2

ο I PO(OH)； 23 200 914254ο I PO(OH); 23 200 914254

• uuC• uuC

[化學式17][Chemical Formula 17]

24 200914254 [化學式18] B—14 CH9—CH.24 200914254 [Chemical Formula 18] B-14 CH9-CH.

CH〇-CH B-15 Γ B-16CH〇-CH B-15 Γ B-16

HN HO, •CH〇—CH-HN HO, •CH〇—CH-

CH〇—CHCH〇—CH

OH B-17OH B-17

CH〇 —CH CH3 I 、 CH〇-C —— 〇 25 200914254CH〇—CH CH3 I , CH〇-C —— 〇 25 200914254

[化學式19][Chemical Formula 19]

CH2 —CHCH2 — CH

00

S i (OCHg)S i (OCHg)

ch2Ch2

po(oh)2 (q = 4與q = 5之混合物） 26 200914254 [化學式20] B-21Po(oh)2 (a mixture of q = 4 and q = 5) 26 200914254 [Chemical Formula 20] B-21

CH2 —CH- W 0 HOCH2 —CH- W 0 HO

(q = 4與q = 5之混合物） 27 2 00914254 [化學式21] B-24 B —25(q = 4 and q = 5 mixture) 27 2 00914254 [Chemical Formula 21] B-24 B -25

CH, CH.CH, CH.

B-26B-26

對位/間位=1/1 B-27 /〇 (II 0 aAlignment/Interval=1/1 B-27 /〇 (II 0 a

對位/間位=1/1 B-28 〇Alignment/Interval=1/1 B-28 〇

〇 t°OI〇-〇-c H°〇 t°OI〇-〇-c H°

Si(OCH〇) V% 28 200914254 ▲·夕丄‘· I 2-^J-X· 熱塑H (1)可為上述熱塑性聚合物之一個種類或兩個或兩個以上麵之混合物。另外，物⑴ 可與熱塑性聚合物⑵叹/_紐聚合物⑶混合。熱塑性聚合物（2)Si(OCH〇) V% 28 200914254 ▲·夕丄'· I 2-^J-X· Thermoplastic H (1) may be one type of the above thermoplastic polymer or a mixture of two or two of the above. Further, the substance (1) may be mixed with the thermoplastic polymer (2) stagnation/_new polymer (3). Thermoplastic polymer (2)

—本發明中所用之熱塑性聚合物⑺在主鏈末端之至少刀中具有w夠與無機細㈣成化學鍵之官能基。所述可存在於一個或兩個主鏈末端中。然而，官能基較 t僅存在於—艇鏈末财。乡個讀基可存在於主鏈末中。线末端”是指不包括重複單元以及重複單元之 =所***之結構的聚合物部分。“化學鍵，，被視作與上述熱塑性聚合物（1)中之化學鍵類似。能夠與無機細粒形成化學鍵之官能基為由以下基團中選出者： [化學式22] OR21 OR23- The thermoplastic polymer (7) used in the present invention has a functional group capable of forming a chemical bond with an inorganic fine (tetra) in at least a knives at the end of the main chain. The may be present in one or both of the backbone ends. However, the functional group is only present in t-boat chain. A rural reading base can exist in the end of the main chain. "End of line" means a polymer portion excluding the repeating unit and the structure of the repeating unit = "chemical bond", which is considered to be similar to the chemical bond in the above thermoplastic polymer (1). The functional group capable of forming a chemical bond with the inorganic fine particles is selected from the following groups: [Chemical Formula 22] OR21 OR23

I I —- P — OR^ 一 0 P — Or24 II II 〇、 0 [R21、R22、R23以及R24之每一者可為氫原子、經取代或未經取代之烧基、經取代或未經取代之稀基、經取代或未經取代之炔基或經取代或未經取代之芳基的任一者；|、 -S〇3H、-0S03H、-C〇2H 以及-Si(OR25)m2R263 m2[R25 以及 R26之每一者為氫原子、經取代或未經取代之烷基、經取代或未經取代之烯基、經取代或未經取代之块基或經取代或 29 200914254 未經取代之芳基，且m2為i至3之整數在 R 、R 2、R2'、R、4、R25 以及 r26 之—— 代或未經取代之絲、經取代或未經取代之=者為經取，經取代之絲或經2取代或未經取代之芳基^情‘一、R25以及R26之較佳碳原子數II —- P — OR^ — 0 P — Or24 II II 〇, 0 [R21, R22, R23 and R24 each may be a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted Any of a dilute, substituted or unsubstituted alkynyl group or a substituted or unsubstituted aryl group; |, -S〇3H, -0S03H, -C〇2H, and -Si(OR25)m2R263 m2 [R25 and R26 are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted block group or substituted or 29 200914254 unsubstituted An aryl group, and m2 is an integer from i to 3, wherein R, R 2, R 2 ', R, 4, R 25 and r 26 are substituted or unsubstituted, substituted or unsubstituted = The preferred carbon number of the substituted filament or the substituted or unsubstituted aryl group I, R25 and R26

R 、R22、R23、R 況下，、官能基以及取代基與R”、R]2、R13、r14、Rl5以及Rl6之較佳In the case of R, R22, R23 and R, the functional group and the substituent are preferably the same as R", R]2, R13, r14, Rl5 and Rl6.

碳原子數、官能基以及取代基相同。m2較佳為3。在上述官能基中，較佳者為：[化學式23] OR21I ~~ P ——OR22II 〇 OR23I 0 — P — OR24II 〇 •S〇3H、-C〇2H 以及-Si(〇R25)m7R263m2。更佳官能基為： [化學式24] "The number of carbon atoms, the functional group, and the substituent are the same. M2 is preferably 3. Among the above functional groups, preferred are: [Chemical Formula 23] OR21I ~~ P - OR22II 〇 OR23I 0 - P - OR24II 〇 • S〇3H, -C〇2H and -Si(〇R25)m7R263m2. The preferred functional group is: [Chemical Formula 24] "

OR21OR21

P— OR 22 0 OR23I 〇 — P — OR24II o 30 200914254 厶7 i厶* 。尤繼之官能基為： OR23 I 0 —P— OR24 OR21P—OR 22 0 OR23I 〇 — P — OR24II o 30 200914254 厶7 i厶* . The functional base of You Ji is: OR23 I 0 —P— OR24 OR21

I OR22 0 o 以及-8〇3η。本發明中熱塑性聚人限制。可使用孰知之基本骨架並未受到特別聚苯乙婦、聚ί稀結:^聚(甲基)_、酯、聚胺基甲酸酯、取來方酗（polyaiylate)、聚碳酸聚硫趟、環歸煙 ^ώ亞胺、聚驗、聚醚石風、聚_同、聚合物 '聚芳:以:含聚物之結構。乙烯基乙烯基聚合物為争社、土團之聚碳酸酯為較佳的，且所述者相同。'、、土、4寸疋貫例與關於熱塑性聚合物（1) 本發明中所用之熱塑性聚合更大、更估ΐςς·+、* 、角竽乂佳1.50或 .或更大、進一步較佳1.60 λ Η # 較佳1.65或更大之拍^ ^ 及吏大且尤其貝折料d ·之折射率是使用阿 (Abbes refractometer) (Atago , j . DR-M4)藉由5δ9奈米波長之入射光進行量測。儿. 本發明中所用之熱塑性聚合物（2)具有較佳5〇它至 4〇(TC且更佳801：至38(rc之玻璃轉移溫度。若熱^性聚人物（2)具有至少5(TC之玻璃轉移溫度，則耐熱^增加: 右熱塑性聚合物（2)具有至多400°C之破ϊ离轉移㈤产，則 31 200914254 ^yiz^fpir.aoc 易於加工 ===ί細在⑽奈米波長下 8〇G/°之透光度，且在厚度為1毫米之情況下具有較佳至少更佳至少85%之透光度。 ^ 本發明中所用之熱塑性聚合物⑵具 500,000之數量平均分子量。數^ L000至 ^ 0八十均刀子置較佳為3,〇〇〇至 300,000 ,更<土為 5,000 | 2〇〇,〇〇〇，且I OR22 0 o and -8〇3η. Thermoplastic polymerization is limited in the present invention. The basic skeleton that can be used without knowing is not subject to special polystyrene, poly (thick), poly(methyl)-, ester, polyurethane, polyaiylate, polyaluminum polysulfide环归 ώ ώ ώ ώ ώ 聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚聚醚聚醚聚醚聚醚聚醚聚醚聚醚聚醚聚醚聚醚The vinyl vinyl polymer is preferred as the colloidal, earthy polycarbonate, and the same. ',, soil, 4 inch cross-section with respect to the thermoplastic polymer (1) The thermoplastic polymerization used in the present invention is larger, more estimated ΐςς·+, *, angle 1.5 1.50 or more, further preferably 1.60 λ Η # 最好 1.6 or larger 拍 ^ ^ and 吏 and especially the beryllium d · The refractive index is the use of Ab (Abs refractometer) (Atago, j. DR-M4) by 5δ9 nm wavelength The incident light is measured. The thermoplastic polymer (2) used in the present invention has a glass transition temperature of preferably from 5 至 to 4 〇 (TC and more preferably from 801: to 38 (r) if the thermal group (2) has at least 5 (TC glass transition temperature, then heat resistance ^ increase: right thermoplastic polymer (2) has a breakup transfer of up to 400 ° C (five) production, then 31 200914254 ^yiz^fpir.aoc easy to process === 细细 at (10) Transmittance of 8 〇 G/° at a nanometer wavelength, and preferably at least 85% transmittance at a thickness of 1 mm. ^ The thermoplastic polymer (2) used in the present invention has 500,000 The number average molecular weight. The number ^ L000 to ^ 0 80 knives is preferably set to 3, 〇〇〇 to 300,000, and more < soil is 5,000 | 2 〇〇, 〇〇〇, and

擊至摩。藉由使用數量平均分子量為至二為〇提升熱塑性之熱塑性聚合物⑵，增加機械強度。藉由使職量平均分子量為至多500,000之熱塑性聚合物（2 聚合物（2)之加工性改良。將官能基引入主鏈末端中之方法並未受到特別限制。舉例而言，如由曰本高分子學會（Society of P〇lymer Science, Japan)編輯之"New Polymer Experimental Studies 4, Synthesis and Reaction of Polymer (3) Reaction and Decomposition of p〇lymer”的第3章末端反應性聚合物 (Terminal Reactive Polymer)中所述，可在聚合時或在聚合後引入官能基。在聚合後引入官能基之情況下，聚合物經分離且隨後經受末端官能基轉化或主鏈分解。亦有可能使用聚合物反應，諸如藉由使用具有官能基以及/或經保護官能基之引發劑、終止劑、鏈轉移劑（chain transfer agent) 或其類似物進行聚合以人成聚合物之方法；以及兩含吕能基之反應劑修飾由（例如）雙酚A合成的聚碳酸酯之酚末端基團之方法。舉例而言，可列舉使用由日本高分子學會 200914254Hit to the motorcycle. The mechanical strength is increased by using a thermoplastic polymer (2) having a number average molecular weight of up to two to increase the thermoplasticity. By modifying the thermoplasticity of the thermoplastic polymer having a mean molecular weight of at most 500,000 (2 polymer (2). The method of introducing a functional group into the end of the main chain is not particularly limited. For example, Chapter 3 End-Reactive Polymers (Terminal, edited by Society of P〇lymer Science, Japan, "New Polymer Experimental Studies 4, Synthesis and Reaction of Polymer (3) Reaction and Decomposition of p〇lymer The functional group may be introduced during or after the polymerization as described in Reactive Polymer. In the case where a functional group is introduced after the polymerization, the polymer is separated and subsequently subjected to terminal functional group conversion or main chain decomposition. It is also possible to use polymerization. Reaction, such as by using a functional group and/or a functional group having a protective functional group, a terminator, a chain transfer agent, or the like, to polymerize to form a polymer; and The reactants modify the phenolic terminal group of the polycarbonate synthesized by, for example, bisphenol A. For example, the use of the day may be cited. Society of Polymer Science 200 914 254

jju.uuC (Society of Polymer Science, Japan)編輯之nNew PolymernNew Polymer edited by jju.uuC (Society of Polymer Science, Japan)

Experimental Studies 2, Synthesis and Reaction.of Polymer (1) Synthesis of Addition-Type Polymer”之第 110-112 頁中所述的含硫鏈轉移劑由鏈轉移方法進行之乙烯基單體的自由基聚合；使用由日本高分子學會（Society of Polymer Science, Japan)編輯之"New Polymer Experimental Studies 2, Synthesis and Reaction of Polymer (1) Synthesis of Addition-Type Polymer”之第255-256頁中所述的含官能基之引發劑以及/或含官能基之終止劑的活性陽離子聚合；以及使用 Macromolecules,第 36 卷，（2003)之第 7020-7026 頁中所述之含硫鏈轉移劑的開環複分解聚合。在下列說明化合物P-1至卩_22中描述可用於本發明中之熱塑性聚合物（2 )的較佳特定貫例，但熱塑性聚人物（2 ) 並不限於此等實例。括號中之結構表示重複單元，°且重複單元之“X”與“y”表示共聚比（莫耳比）。 200914254 zyi/^pii.aoc [化學式26] P—1 Η· ch-ch2Ts-ch2ch2opo3h2Experimental Study 2, Synthesis and Reaction. of Polymer (1) Synthesis of Addition-Type Polymer" on the pages 110-112 of the sulfur-containing chain transfer agent is a free radical polymerization of a vinyl monomer by a chain transfer method; The use of the content described in pages 255-256 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 of functional group initiators and/or functional group-containing terminators; and ring-opening metathesis polymerization using sulfur chain transfer agents as described in Macromolecules, Vol. 36, (2003), pp. 7020-7026 . Preferred specific examples of the thermoplastic polymer (2) usable in the present invention are described in the following description of the compounds P-1 to 卩22, but the thermoplastic poly-man (2) is not limited to these examples. The structure in parentheses indicates a repeating unit, and "X" and "y" of the repeating unit indicate a copolymerization ratio (mole ratio). 200914254 zyi/^pii.aoc [Chemical Formula 26] P-1 Η·ch-ch2Ts-ch2ch2opo3h2

P-2 ch-ch2- l I 1. NP-2 ch-ch2- l I 1. N

s-ch2ch2opo3h2 s-ch2ch2opo3h2 P-4 h3co 丁ch-ch2--ch —〇ch2ch2ch2co2h .och3 ch3S-ch2ch2opo3h2 s-ch2ch2opo3h2 P-4 h3co butyl ch-ch2--ch —〇ch2ch2ch2co2h .och3 ch3

34 200914254 2yi/4pn.aoc [化學式27] P-834 200914254 2yi/4pn.aoc [Chemical Formula 27] P-8

P. CH-CH,P. CH-CH,

S-CH2CH2OPOsH2S-CH2CH2OPOsH2

Br P-11 H Br P-10Br P-11 H Br P-10

s-ch2ch2opo3h2 ch-ch2- B rS-ch2ch2opo3h2 ch-ch2- B r

B r S-CH2CH2〇P03H2B r S-CH2CH2〇P03H2

P-12 H- ch3 c-ch2 I CH, J V o^nao L 1 - y SCH2CH2OP〇3H2 ch3 x : y =50: 50 35 200914254P-12 H- ch3 c-ch2 I CH, J V o^nao L 1 - y SCH2CH2OP〇3H2 ch3 x : y =50: 50 35 200914254

IZH-pii.UUCIZH-pii.UUC

[化學式28] P-13 (H3C0)3 SiH2CH2CH2CS - CH-CH2 o丄ΟP-13 (H3C0)3 SiH2CH2CH2CS - CH-CH2 o丄Ο

Ph P-14 ch-ch2-Ph P-14 ch-ch2-

ch3 CH - C02CH3Ch3 CH - C02CH3

、〇ro3H2 P-15 ho3sh2ch2c· P-16,〇ro3H2 P-15 ho3sh2ch2c· P-16

ch3 〇-o-O+^o1 CHS ch3 〇O+-^-〇ch2CH2s〇3H CH, ( ~Bu CH-j— CH2CH2OPO3H2 P-17Ch3 〇-o-O+^o1 CHS ch3 〇O+-^-〇ch2CH2s〇3H CH, ( ~Bu CH-j- CH2CH2OPO3H2 P-17

0-^>-S03H 36 200914254 zy lZH-pn.aoc [化學式29]0-^>-S03H 36 200914254 zy lZH-pn.aoc [Chemical Formula 29]

s-ch2ch2〇po3h2 s-ch2ch2op〇3h2 P-20S-ch2ch2〇po3h2 s-ch2ch2op〇3h2 P-20

s -B u CH2—CH 0s -B u CH2—CH 0

0 00 0

a 、0H 〇 0 CH2CH20 —_.S 〇3ha , 0H 〇 0 CH2CH20 — _.S 〇 3h

P-22P-22

-0 O^〇so3k 可使用上述熱塑性聚合物（2)之—個個以上種類之、、Θ入铷^ 犬員戍兩個或兩共聚組Γ 4_性聚合物⑺可含有其他 37 200914254 zvizHpu.uoc 熟塑性聚合物為由巯水性段（A) 本發明中所用之熱塑性聚合物（與親水性段（B)構成之嵌段共聚物_ 疏水性段（A)構成不溶於水或甲醇中水性段（B )構成可溶於水與甲醇之至少_ 來5物親嵌段共聚物之類型包括AB型、B]AB2 之聚合物。在B]AB2型中，兩個親水性段Βι與B2 A BA型。在A!BA2型中，兩個疏水性段Ai|八2可目同或不同。馨於分散性的考量，AB型或A]BA〜H同或不同。佳的。雲於製造適宜性的考量，AB =共聚物為較水性段A】與A2相同之心八2型）為較型（兩個疏尤其較佳的。 9 ’且AB型為疏水性段（A)以及親水性段⑻ > ^聚合物’諸如藉由乙稀基單體之聚合而可選自， 3物、聚ϋ、開環複分解聚合聚合物乙烯基聚 :旨:聚醋、聚醯胺、聚醚_、聚_風以及=物，炭酸 =之，乙烯絲合物、開環複分合物）。 _及聚料健的。#於製造適宜性物、聚碳酸乙^%基聚合物。里’更佳的為形成疏水性段（Α)之乙稀基單列單體：__旨1基_動旨（㈣2實例包括下 :代:脂族，基或經取代或未經取代之J族二取代或未經土 '苯基、萘基或其類似基團）；矢―9基’例如甲嘛胺、甲基輪胺，更特定言之… Ν早取代丙 38 200914254-0 O^〇so3k can be used as the above-mentioned thermoplastic polymer (2), more than one type, intrusive 铷^ canine 戍 two or two copolymerized groups Γ 4_ polymer (7) can contain other 37 200914254 zvizHpu .uoc mature plastic polymer is composed of hydrophobic polymer (A). The thermoplastic polymer used in the present invention (block copolymer composed of hydrophilic segment (B) _ hydrophobic segment (A) is insoluble in water or methanol. The aqueous section (B) constitutes a polymer which is soluble in at least 5 types of water and methanol, and includes a type AB, B]AB2. In the B]AB2 type, two hydrophilic segments Βι and B2 A BA type. In the A!BA2 type, the two hydrophobic segments Ai|8 can be the same or different. In terms of dispersibility, AB or A]BA~H are the same or different. For the consideration of manufacturing suitability, AB = copolymer is the more water-soluble segment A] and A2 is the same as A2) (the two are particularly preferred. 9 ' and AB is the hydrophobic segment (A) And the hydrophilic segment (8) > ^ polymer 'such as by polymerization of ethylene monomer can be selected, 3, polyfluorene, ring-opening metathesis polymer polymer vinyl poly: Purpose: Polyacetate, polyamide, polyether _, poly _ wind and =, carbonic acid =, vinyl complex, ring-opening complex). _ and gathering materials are healthy. #于制造性性性, Polycarbonate Ethyl polymer. More preferably, it is a silicon-based single-row monomer which forms a hydrophobic segment (Α): __一基基_动((4) 2 Examples include the following: generation: aliphatic, radical or substituted or unsubstituted J A group of disubstituted or unsubstituted tert-phenyl, naphthyl or the like; a -9-yl group such as methylamine, methylamine, more specifically... 取代 early replacement of C38 200914254

z：/ iznpu.uvjC 烯醯胺、N-二取代丙焯胺、N-單取代甲基丙烯醯二取代曱基丙烯醯胺（單取代產物以及二取代產^ 、N' 基包括經取代或未經取代之脂族基團以及經取代咬未=代代之芳族基團，例如甲基、笨基、萘基或其類似^團 Γ'z:/ iznpu.uvjC eneamine, N-disubstituted propionamide, N-monosubstituted methyl propylene hydrazine disubstituted mercapto acrylamide (monosubstituted products and disubstituted products, N' groups including substituted or Unsubstituted aliphatic groups and substituted aromatic groups such as methyl, stupyl, naphthyl or the like

烯烴，更特定言之，二環戊二烯、降冰片烯ς生物’、乙烯、丙烯、1-丁烯、1-戊烯、乙烯基氯、偏二氯乙烯、異戊二烯、氯丁二烯、丁二烯、2,3-二甲基丁二烯以及乙烯基咔唑；苯乙烯類，更特定言之，笨乙烯、甲基笨乙歸、二甲基苯乙烯、三甲基苯乙烯、乙基苯乙烯、^丙基笨乙烯、氯甲基苯乙烯、曱氧基苯乙烯、乙醯氧基苯乙烯、氯苯乙細、一乳本乙細、溴本乙細、三溴苯乙稀以及乙稀^ 苯甲酸甲酯；以及土乙烯基醚類，更特定言之，曱基乙烯基醚、丁基乙烯基醚、苯基乙烯基醚以及甲氧基乙基乙烯基醚；其他單體，諸如丁烯酸丁酯、丁烯酸己酯、衣康酸二甲酯、衣康酸二丁酯、順丁烯二酸二乙酯、順丁稀二酸二甲酯、順丁稀二酸二丁酯、反丁烯二酸二乙酯、反丁烯二酸二甲酯、反丁烯二酸二丁酯、甲基乙烯基酮、苯基乙烯基酮、曱氧基乙蒸乙却基I同、Ν-乙細基σ惡Π坐炫(g同、Ν-乙稀基。比17各σ定晒、偏二氯乙烯、亞甲基丙二腈、亞乙烯基、碟酸二苯基_2-丙烯醯氧基乙醋、磷酸二苯基-2-曱基丙烯醯氧基乙酯、磷酸二丁基-2-丙烯酸氧基乙酯以及_酸二辛基_2_甲基丙烯醯氧基乙酯。詳言之，酯基為未經取代之脂族基團或經取代或未經 39 200914254 29124pii.doc 取代之芳知基團之丙烯酸酯以及甲基丙烯酸酯；取代基為未、，取代之脂絲團錢取代絲經取狀芳族基團二〆單取代丙稀醯月女、N-一取代丙烯醯胺、N_單取代甲基丙烯酿胺以及N_二取代甲基丙烯酸胺；以及苯乙稀類為較佳的。自日基為經取代或未經取代之芳族基團之丙烯酸酯以及甲基丙烯酸酯；以及苯乙烯類為更佳的。。。形成親水性段（B)之乙烯基單體（b)之實例包括下 =單體.在酯部分上具有親水性取代基之丙烯酸、甲基丙烯酸、丙烯酸酯以及甲基丙烯酸酯；在芳環上具有親水性取代基之苯乙烯類；具有親水性取代基之乙烯基鱗、丙烯醯胺、曱基丙烯醯胺、N-單取代丙烯醯胺、N-二取代丙烯醯胺、N-單取代曱基丙烯醯胺以及N_二取代曱基丙烯醯胺。親水性取代基較佳具有由以下各基團所構成的族群中選出之官能基：Olefins, more specifically, dicyclopentadiene, norbornene, bio-, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene Diene, butadiene, 2,3-dimethylbutadiene and vinyl carbazole; styrene, more specifically, stupid ethylene, methyl stupor, dimethyl styrene, trimethyl Styrene, ethyl styrene, propyl styrene, chloromethyl styrene, decyloxy styrene, ethoxylated styrene, chlorostyrene, acetonide, bromine, fine Bromostyrene and ethyl benzoate; and soil vinyl ethers, more specifically, mercapto vinyl ether, butyl vinyl ether, phenyl vinyl ether, and methoxyethyl vinyl Ether; other monomers, such as butyl butenoate, hexyl butenoate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl butyl succinate , dibutyl succinate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, hydrazine oxygen Ethyl bromide I, Ν-B-based σ Π Π 炫 ( (g with the same, Ν-ethylene base. Compared with 17 σ 定 sun, vinylidene chloride, methylene malononitrile, vinylidene , dish diphenyl-2-propenyloxyacetate, diphenyl-2-mercaptopropenyloxyethyl phosphate, dibutyl-2-ethyl acrylate and tic acid dioctyl _2_Methyl propylene methoxyethyl ester. In particular, the ester group is an unsubstituted aliphatic group or an acrylate and a methyl group substituted or not substituted by 39 200914254 29124pii.doc Acrylate; the substituent is unsubstituted, the substituted aliphatic filaments are substituted for the silk, and the aromatic group is substituted by di-monosubstituted propylene, the N-substituted decylamine, and the N-monosubstituted methyl propylene. Amines and N-disubstituted methacrylic acid amines; and styrene are preferred. Acrylates and methacrylates which are substituted or unsubstituted aromatic groups from the group; and styrenes More preferably, examples of the vinyl monomer (b) forming the hydrophilic segment (B) include lower = monomer. acrylic acid, methacrylic having a hydrophilic substituent on the ester moiety , acrylates and methacrylates; styrenes having a hydrophilic substituent on the aromatic ring; vinyl scales having a hydrophilic substituent, acrylamide, mercaptopropenamide, N-monosubstituted acrylamide , N-disubstituted acrylamide, N-monosubstituted decyl acrylamide, and N-disubstituted decyl acrylamide. The hydrophilic substituent preferably has a functional group selected from the group consisting of the following groups; :

[化學式30][Chemical Formula 30]

0R& ! ο—P—OR OR31 34 —P—OR320R& ! ο—P—OR OR31 34 —P—OR32

II 0 〇 [R·31、R32、R/3以及R34之每一者可為氫原子、經取代或未經取代之烷基、經取代或未經取代之烯基、經取代或未經取代之炔基或經取代或未經取代之芳基的任一者]、，S03H、-〇S〇3H、-C02H、-OH 以及-Si(〇R35)m3R363-m3[R35 以及R°6之每一者為氫原子、經取代或未經取代之院基、 40 200914254 ^yi^4pu.aoc 經取代或德取代之縣、經取代或未經取代之芳基，且m3戈或未經取代之炔基或經若 R3]、R32、R33、R34、r35' 1 至 3 之整 ^:]。代或未經取代之絲、經之每-者為經取 =取，基或經取II 0 〇 [R·31, R32, R/3 and R34 each may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, substituted or unsubstituted Any of alkynyl or substituted or unsubstituted aryl groups], , S03H, -〇S〇3H, -C02H, -OH, and -Si(〇R35)m3R363-m3 [R35 and R°6 Each is a hydrogen atom, a substituted or unsubstituted aryl group, 40 200914254 ^yi^4pu.aoc substituted or desubstituted aryl, substituted or unsubstituted aryl, and m3 ge or unsubstituted The alkynyl group or the entire group of R3], R32, R33, R34, r35' 1 to 3:]. Generation or unsubstituted silk, each of which is taken, taken, taken or taken

R 、R以及R，之較佳碳原子數、官能基以及取代基與R】1 H Rl3、R】4、Rl5 及Rl6之較佳石炭原子數、官能基以及取代基相同。m3較佳為3。吕能基較佳為： [化學式31] OR31 OR33R, R and R preferably have the same number of carbon atoms, functional groups and substituents as those of R]1 H Rl3, R 4, Rl5 and R16 which are preferably the same number of carbon atoms, functional groups and substituents. M3 is preferably 3. Lunengji is better: [Chemical Formula 31] OR31 OR33

I I —P—OR32 _〇—P—〇R34 II lX 〇、 0 -C〇2H 4-Si(OR35)m3R363-m3，且更佳為 [化學式32] OR31 〇R33 —P—OR32 —0—P—OR34II —P—OR32 _〇—P—〇R34 II lX 〇, 0 -C〇2H 4-Si(OR35)m3R363-m3, and more preferably [Chemical Formula 32] OR31 〇R33 —P—OR32 —0—P —OR34

II A 〇 0 、 41 200914254II A 〇 0 , 41 200914254

‘7 上丄.uuC 以及-C02H，且尤其較佳為 [化學式33] 2 3 R o R0Ii o — p no o Μ R 〇 331 R I o ——ΡΠΜΟ 在本發明中，嵌段共聚物較佳具有選自以下基團之官能基： [化學式34] OR31 —P—OR32 — II 〇 OR33 I 34 Ο—P—OR34'7 上丄.uuC and -C02H, and particularly preferably [Chemical Formula 33] 2 3 R o R0Ii o — p no o Μ R 〇 331 RI o —— ΡΠΜΟ In the present invention, the block copolymer preferably has A functional group selected from the group consisting of: [Chemical Formula 34] OR31 - P - OR32 - II 〇 OR33 I 34 Ο - P - OR34

II 〇、 -S03H、-0S03H、-C02H、-OH 以及-Si(OR35)m3R363.m3，且官能基之含量為至少0.05毫莫耳/公克且至多5.0毫莫耳 /公克。詳言之，親水性段（B)較佳為在酯部分上具有親水性取代基之丙烯酸、曱基丙烯酸、丙烯酸酯或曱基丙烯酸酯；以及在芳環中具有親水性取代基之苯乙烯。由乙烯基單體（a)形成之疏水性段（A)亦可在不改變疏水性質之範圍内含有乙烯基單體（b)。疏水性段（A) 中所含之乙烯基單體（a)與乙烯基單體（b)之間的莫耳比較佳為100:0至60:40。由乙烯基單體（b)形成之親水性段（B)亦可在不改變親水性質之範圍内含有乙烯基單體（a)。親水性段（B) 42 200914254 29124pif.doc 乙烯基單體（b)與乙稀基單體（a)之間的比較佳為1〇〇:〇至6〇:4〇。 $吳耳乙烯基單體（a)以及（b)之每一者以上種類之單體組成。根據目的(舉 f:酉夂:：、調節玻璃轉移溫度（Tg)、調節有機溶；充以及（b)。乃即刀月文％疋性）來選擇乙婦基單體（a) 相對於嵌段共聚物之總量而 0.05毫莫耳/公克至5.0毫莫耳/公克，且更為 /公克至4.5毫莫耳/八自 …·耄莫耳至h亳料"ίΓ。二，二，為°.15毫莫耳/公克可能降低。若量過低’則分散適宜性高或有機會變得過 …i 共聚物中，官能基可與諸如驗金屬齡 •山a、K或其類似離子）或銨離子之陽離子形成趨甘欠段共聚物之數量平均分子量 /成^。 _。數000 ’且尤其較佳為_至定分散液。數量平二八:=^000之嵌段共聚物形成穩加有機溶齊置為至多100000之栽段共聚物增更大nr用之嵌段共聚物之折射率較佳為w或且/iti為1,55或更大’進—步較佳為1也戈更大二大。本文中所用之折射率=阿 (tag0之產品，型號：DR_M4)藉由測奈米 200914254 29124piI.a〇c 波長之入射光進行量測。本發明中所用之嵌段共聚物之玻璃轉移溫度較佳在 80t至400°C之範圍内，且更佳為130°C至380°C。玻璃轉移溫度為至少8 0 °C之嵌段共聚物增加耐熱性。玻璃轉移溫度為至多400°C之嵌段共聚物改良加工性。本發明中所用之嵌段共聚物較佳具有在厚度為1毫米之情況下在589奈米之波長下量測之至少80%的光學透射率。光學透射率更佳為至少85%。下文列出嵌段共聚物之特定實例（說明性化合物P1 至P20)。然而，本發明中所用之嵌段共聚物並不限於下列特定實例。II 〇 , -S03H, -0S03H, -C02H, -OH and -Si(OR35)m3R363.m3, and the content of the functional group is at least 0.05 millimoles/gram and at most 5.0 millimoles/gram. In particular, the hydrophilic segment (B) is preferably acrylic acid, mercaptoacrylic acid, acrylate or mercapto acrylate having a hydrophilic substituent on the ester moiety; and styrene having a hydrophilic substituent in the aromatic ring. . The hydrophobic segment (A) formed of the vinyl monomer (a) may also contain the vinyl monomer (b) within a range not changing the hydrophobic property. The molar amount between the vinyl monomer (a) and the vinyl monomer (b) contained in the hydrophobic segment (A) is preferably from 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 not changing the hydrophilic property. Hydrophilic segment (B) 42 200914254 29124pif.doc The comparison between the vinyl monomer (b) and the ethylene monomer (a) is preferably 1 〇〇: 〇 to 6 〇: 4 〇. $吴耳 Each of the above types of vinyl monomers (a) and (b). According to the purpose (f: 酉夂::, adjust the glass transfer temperature (Tg), adjust the organic solution; charge and (b). That is, the knife and the moon), select the ethylenic monomer (a) relative to The total amount of block copolymer is from 0.05 millimoles per gram to 5.0 millimoles per gram, and more / gram to 4.5 millimoles / eight from ... 耄耳至 to h 亳 & & & Γ Γ Γ. Two, two, for °. 15 millimoles / gram may be lowered. If the amount is too low, then the dispersion is highly suitable or there is a chance to become...I, in the copolymer, the functional group can form a stagnation segment with a cation such as metal age, mountain a, K or the like) or ammonium ion. The number average molecular weight of the copolymer / is ^. _. A number of 000 ' and particularly preferably _ is a dispersion. The number of flat blocks: = ^ 000 block copolymer forms a stable organic solvent set to a maximum of 100,000 of the copolymer, the refractive index of the block copolymer is preferably w or / / iti 1,55 or more 'into the step is better than 1 and the second is bigger. The refractive index used in this article = A (product of tag 0, model: DR_M4) is measured by measuring the incident light of the wavelength of nanometer 200914254 29124piI.a〇c. The glass transition temperature of the block copolymer used in the present invention is preferably in the range of from 80 t to 400 ° C, and more preferably from 130 ° C to 380 ° C. Block copolymers having a glass transition temperature of at least 80 °C increase heat resistance. The block copolymer having a glass transition temperature of at most 400 ° C improves the processability. The block copolymer used in the present invention preferably has an optical transmittance of at least 80% measured at a wavelength of 589 nm with a thickness of 1 mm. The optical transmittance is more preferably at least 85%. Specific examples of the block copolymers (illustrative compounds P1 to P20) are listed below. However, the block copolymer used in the present invention is not limited to the following specific examples.

C 44 200914254 29124pii.doc [表1]C 44 200914254 29124pii.doc [Table 1]

45 20091425445 200914254

么_/ 1 二-τρι 丄.vuv^C__ 1 two-τρι 丄.vuv^C

[表2] 編號 ------- -~~~~~— 莫耳 % —B — 莫耳 % 分子量 P-13 90 ^cr c〇2H 10 35000 P-14 95 OPO3H2 5 30000 P-15 80 20 31000 P-16 95 OPO3H2 5 29000 P-17 88 CO2H 12 33000 P-18 & 90 0P03H2 10 28000 P-19 85 c〇2H 15 35000 P-20 I —~~-— 93 飞〇p〇3H2 7 36000 利用活性自由基聚合以及活性離子聚合以及必要時保護叛基或向聚合物中引入官能基之技術來合成嵌段共聚物。亦有可能藉由具有末端官能基之聚合物的自由基聚合以及在具有末端官能基之聚合物之間形成鍵來合成嵌段共聚物。詳言之，鑒於分子量控制以及嵌段共聚物之產率，較佳利用活性自由基聚合以及活性離子聚合。嵌段共聚物之製造方法描述於（例如）由日本高分子學會（The Society of Polymer Science, Japan)編輯且由 Kyoritsu Shuppan Co., Ltd. (1992 年）出版之"Synthesis and reaction of polymer 46 200914254 zyi^^pn.aoc[Table 2] No. ------- -~~~~~ - Moer % - B - Molar % Molecular Weight P-13 90 ^cr c〇2H 10 35000 P-14 95 OPO3H2 5 30000 P-15 80 20 31000 P-16 95 OPO3H2 5 29000 P-17 88 CO2H 12 33000 P-18 & 90 0P03H2 10 28000 P-19 85 c〇2H 15 35000 P-20 I —~~-— 93 Flying 〇p〇3H2 7 36000 The block copolymer is synthesized by a technique of living radical polymerization and reactive ion polymerization, and if necessary, protecting a tether or introducing a functional group into a polymer. It is also possible to synthesize a block copolymer by radical polymerization of a polymer having a terminal functional group and formation of a bond between polymers having terminal functional groups. In particular, in view of molecular weight control and the yield of the block copolymer, living radical polymerization and living ion polymerization are preferably utilized. A method for producing a block copolymer is described, for example, in "The Society of Polymer Science, Japan" and published by Kyoritsu Shuppan Co., Ltd. (1992) "Synthesis and reaction of polymer 46". 200914254 zyi^^pn.aoc

ί (1)";由曰本化學會（Chemical Society of Japan )編輯且由 Japan Scientific Societies Press (1993 年）出版之"Precision polymerization” ；由曰本高分子學會（The Society of Polymer Science, Japan) '編輯且由 Kyoritsu Shuppan Co., Ltd. (1995 年）出版之"Synthesis reaction of polymer (1)” ； R. Jerome 等人，"Progress in Polymer Science",第 16 卷(1991 年）之第 837-906 頁中之'Telechelic Polymer: Synthesis, Characterization, and Applications'; Y. Yagci 等人，”Progress inPolymer Science",第 15 卷(1990 年)之第 551-601 頁中之 'Light-induced synthesis of block and graft copolymers';以及美國專利第5085698號中。 "T使用上述t合物之一個種類或兩個或兩個以上種類之混合物。 [無機細粒] 本發明中所用之無機細粒（無機奈米粒子）包括（例如）氧化物細粒以及硫化物細粒，更特定言之，氧化笋細粒、氧化鋅細粒、氧化鈦細粒、氧化錫細粒以及硫化粒。然而，無機細粒並不侷限於彼等細粒。其中，金二化物細粒為尤其較佳的。詳言之，由氧化錯細粒、^化= 細=氧化锡細粒以及氧化欽細粒所構成的族群中選由氧化錯細粒、氧化鋅細粒以及氧化鈦細粒 :光催化活性以及在可見光區中具有優良透== …田柢=在本發明中’ #純鮮、翻度以及穩定二， 47 200914254 29124pii.doc 可使用兩個或兩個以上種類之上述無機細粒之分散液。為滿足者如降低光催化活性以及吸水率（water abs〇rpti〇n rati:)之目的’上述無機細粒可摻雜有不同種類之元素，且無機細粒之表面可覆蓋有不同金屬氧化物（諸如二氧化石夕以及氧彳⑽）。亦#可制魏偶合劑、㈣鹽偶合劑或其類似物對無機細粒進行表面改質。本發明中所用之無機細粒之製造方法並未受到特別限可使祕何熟知方法。舉例而言，使用 ===，述_在含有水之反應系 ^ 來衣備所品之精細氧化物粒子。特^言之’已知製備氧化錯細粒以及其懸浮液之 ^ :且可制其中任—者：由驗中和含有結鹽之溶液以 :且使所得水合錯乾燥並燒結，隨後，將其分二:厂以製備氧化錯懸浮液之方法二二 :水解以製備氧化嶋液之方法;心; 解，且隨後對所製備之^卜牡鹽谷液水 ^藉此來製備氧化_:==:氧化 ;法向啦鹽之溶液施加壓力來製備氧化例不硫酸氧欽（Tkany丨s祕⑹作 … ,原材料。例示諸如：：=乳化鈦細粒，粒之原材料。諸如四乙氧基二 =鹽作為合成氧孟屬醇鹽亦適用於無機細粒二^異_敛之此#無機細粒之合 48 200914254 成方法包括（例如）Japanese j〇urna】〇f Applied Physjcs，第 37卷（1998年）之第46〇3_46〇8頁以及[如抑此，第l6卷，第1期(2000年)之第241_246頁中所述之方法。詳σ之右氣化物細粒是由溶膠形成法合成的，則有可能使用形成諸如氫氧化物之前驅物，且隨後用酸或驗使所述前驅物脫氫縮合或膠溶，且藉此形成水溶膠之程序，如同使用硫酸氧鈦作為原材料來合成氧化鈦細粒中一樣。 A 纽程序中，最終產物之純度，藉由諸如過濾以及離心分離之任何已知方法將前驅物分離且純化為適當的。所得水溶膠中之溶谬粒子可能不溶於水中，且藉由向水溶膠中添加諸^十二焼基苯顧納（縮寫為Ms)或二院基石黃基丁二酸單鈉鹽（Sanyo Chemical Industries Ltd 之吝口商標名“ELEMIN0LJS_2”）之適當界面活性劑而使:分離。舉例而言，可使用“C〇l〇rMaterial，，，第57卷，6,(1984 年)之第305·308頁中所述之熟知方法。除上述於水中水解之外，亦可例示於有機溶劑中製備 ^( 無機細粒之方法。在此情況下，本發明中所用之熱塑性聚合物可溶解於有機溶劑中。 ’、人、上述方法中所用之溶劑之實例包括丙酮、2-丁酮、二氯曱燒、氯仿、甲苯、乙酸乙酿、環己酉同以及苯甲鍵。; 使用所述溶劑之一個種類或兩個或兩個以上種類之混合物0 、〇若本發明中所用之無機細粒之數量平均粒度（直徑）過小，則可能無法施加形成細粒之無機材料之^有性^， 49 200914254 ^yi/4pir.a〇c 米，更佳為么= 其上限較佳為至多軟铨為至少3奈米，步較佳為至Λ佳為至多10奈米，且進— Γ 數量平均粒度較佳為！太米至中所用之無機細粒之 10奈二且進—步_3奈米至〜7 線繞射量平^度”是使用（例如^ 在饥下，在微鏡（TEM)進行量測。機細粒之折射率较佳在19、 I’本發明中所用之無至2.7之範圍内，且复 ’之範圍内，且更佳在2 〇機細粒之折射率為至多、3乂： 2山】至2.5之範圍内。若無無機細粒與熱紐聚合物之’則瑞雷散射受到抑制，因為機細粒之折射率為至:曰的折射率差異不太大。若無折射率。 .，則所製造之光學透鏡達成高型號一^ 熱塑性聚合物之有機=月中所用之無機細粒以及率且使用單獨量測之熱塑1；^料製成的透明膜之折射測的值來獲得無機細粒之折H勿組份之折射率轉換所量不同濃度之無機細粒分^。亦有可能藉由量測具有射率。刀放液之折射率來計算無機細粒之折 200914254 ^^izH-pn.uoc 人材ΐίϊ:度以及ίΐ高折射率’本發明之有機-無機混材科中無機細粒之含I較佳為20質量％至95 ί 60^〇5 f*%^ 7〇 f *% 5 30 ί i〇/〇 μ 4ΓΛ。在本發明中，#於分散性，無機細粒與熱塑且刀散聚合物之質量比較佳為ι:〇·01幻:1〇〇，更佳為1:0.05至1:10，且尤其較佳為i划5至u。上述有機-無機混合材料（奈米複合材 ·ί (1)";"Precision polymerization" edited by the Chemical Society of Japan and published by Japan Scientific Societies Press (1993); by The Society of Polymer Science, Japan) 'Edited by Kyoritsu Shuppan Co., Ltd. (1995) "Synthesis reaction of polymer (1)”; R. Jerome et al., "Progress in Polymer Science", Volume 16 (1991) 'Telechelic Polymer: Synthesis, Characterization, and Applications'; pp. 837-906; Y. Yagci et al., "Progress in Polymer Science", Vol. 15 (1990), pp. 551-601, 'Light -induced synthesis of block and graft copolymers'; and U.S. Patent No. 5,085,698. "T uses one or a mixture of two or more of the above t compounds. [Inorganic fine particles] used in the present invention The inorganic fine particles (inorganic nanoparticles) include, for example, oxide fine particles and sulfide fine particles, more specifically, oxide fine crystal particles, zinc oxide fine particles, titanium oxide fine particles, Tin fine particles and sulphide granules. However, the inorganic fine granules are not limited to the fine granules. Among them, the bismuth fine granules are particularly preferred. In detail, the oxidized granules are finely oxidized. The group consisting of tin oxide fine particles and oxidized fine particles is selected from the group consisting of oxidized fine particles, zinc oxide fine particles and titanium oxide fine particles: photocatalytic activity and excellent penetration in the visible light region. In the invention '# pure, tumbling and stable two, 47 200914254 29124pii.doc Two or more kinds of the above-mentioned inorganic fine particle dispersion can be used. For satisfying such as reducing photocatalytic activity and water absorption rate (water abs 〇rpti〇n rati:) The purpose of the above inorganic fine particles may be doped with different kinds of elements, and the surface of the inorganic fine particles may be covered with different metal oxides (such as dioxide dioxide and oxonium (10)). The inorganic fine particles may be surface-modified by making a Wei coupling agent, (4) a salt coupling agent or the like. The method for producing the inorganic fine particles used in the present invention is not particularly limited to the method known in the art. For example, using ===, the reaction system containing water is used to prepare the fine oxide particles of the product. Specifically, it is known that the preparation of oxidized fine particles and the suspension thereof can be made into: and the solution containing the salt is prepared and the resulting hydration is dried and sintered, and then, Divided into two: the factory to prepare the oxidative solution suspension method two: hydrolysis to prepare the cerium oxide solution; heart; solution, and then the prepared ^ 卜 salt solution liquid ^ to prepare the oxidation _: ==: Oxidation; normal pressure is applied to the salt solution to prepare oxidized non-sulfate oxysulfate (Tkany 丨s secret (6) for ..., raw materials. For example: :: emulsified titanium fine granules, raw materials of granules such as tetraethoxy Base II = salt as a synthetic oxygen monoxide alkoxide is also suitable for inorganic fine particles. The same is true for this. Inorganic fine grain combination 48 200914254 The method includes (for example, Japanese j〇urna) 〇f Applied Physjcs, 37 Volume 46 (1998), pp. 46〇3_46〇8, and [if this is the case, Volume 16, Volume 1 (2000), pp. 241_246. Detailed σ of the right vaporized fine particles is Synthesized by the sol formation method, it is possible to use a precursor such as a hydroxide, and then use an acid or an assay. The procedure of dehydrogenating condensation or peptization of the precursor, and thereby forming a hydrosol, is the same as using titanium oxysulfate as a raw material for synthesizing titanium oxide fine particles. In the A program, the purity of the final product is filtered by, for example, And any known method of centrifugation separates and purifies the precursor to be appropriate. The solute particles in the obtained hydrosol may be insoluble in water, and by adding to the hydrosol, the oxazolidine (abbreviation) Is a suitable surfactant for Ms) or a compound of the base stone, succinic acid succinic acid monosodium salt (trade name "ELEMIN0LJS_2" of Sanyo Chemical Industries Ltd.): for example, "C〇l〇rMaterial," , Well-known method described in vol. 57, 6, (1984), pp. 305. 308. In addition to the above hydrolysis in water, the method of preparing inorganic fine particles can also be exemplified in an organic solvent. In this case, the thermoplastic polymer used in the present invention can be dissolved in an organic solvent. ', Human, Examples of the solvent used in the above method include acetone, 2-butanone, dichloroanthracene, chloroform, toluene, and B. Ethylene, cyclohexyl and benzoic bond; use one kind of the solvent or a mixture of two or more kinds of the compound 0, 〇 if the average particle size (diameter) of the inorganic fine particles used in the invention is too small , it may not be possible to apply the inorganic material forming the fine particles, 49 200914254 ^yi/4pir.a〇c m, more preferably = the upper limit is preferably at most 3 奈, at least 3 nm, step Jiawei to Jiajia is at most 10 nm, and the inlet- Γ quantity average particle size is better! The inorganic fine particles used in the rice to medium are 10 nanometers and the inward-step _3 nm to ~7 line diffraction amount The flatness is used (for example, ^ under hunger, measured in a micromirror (TEM). The refractive index of the fine particles of the machine is preferably in the range of 19, I' which is used in the present invention, and is in the range of 2.7, and more preferably the refractive index of the fine particles of the 2 〇 machine is at most 3 乂: 2 mountains] to within 2.5. If there is no inorganic fine particles and a thermo-polymer, the Rayleigh scattering is suppressed because the refractive index of the fine particles of the machine is such that the refractive index difference of the crucible is not too large. If there is no refractive index. The optical lens manufactured by the manufacturer achieves the high refractive index of the organic film used in the organic type of the thermoplastic polymer, and the refractive index of the transparent film made by using the separately measured thermoplastic 1; To obtain the refractive index of the inorganic fine particles, the refractive index of the components is converted into inorganic fine particles of different concentrations. It is also possible to measure the radiance by measuring. The refractive index of the knife discharge liquid is used to calculate the folding of the inorganic fine particles. 200914254 ^^izH-pn.uoc Human material ΐ ϊ ϊ 度度度度度度度度 ' ' ' ' ' ' ' ' ' ' ' ' 20% by mass to 95 ί 60^〇5 f*%^ 7〇f *% 5 30 ί i〇/〇μ 4ΓΛ. In the present invention, the quality of the dispersibility, inorganic fine particles and thermoplastic and knife-dispersed polymer is preferably ι: 〇·01 illusion: 1 〇〇, more preferably 1:0.05 to 1:10, and especially Preferably, i is 5 to u. The above organic-inorganic hybrid material (nano composite material

C i ==少一個主鍵末端以及側鍵中具有能;=: =合材料有效地用作光學透鏡之原材料，且:用 1 = 形表面之模具進行射出成形或壓製成形。所製膠=及玻璃透鏡之組合使用有效作 St 早兀之先學組件。下文描述包括由上述奈成之光學透鏡的光料統單元。應注意，各二併入如圖2中所示之行動電話中之數位攝影铋的攝衫光學糸統2之光學系統單元。 [實施例1] 鬧4圖^!_所示之鮮纟統單元由安置於影像側之孔徑光後方之二?鏡5與第二透鏡6組成且安置於孔徑光闌4 之透鏡早凡以及平面平行板7構成。第一透鏡$為由 ^如)甲基丙烯酸酯製成之歸透鏡，且其兩個表面均為 f弟—透鏡6為採用本發明之正光焦度（positive ==:1)之^膠透鏡，且其兩個表面均為非球面。 ’、’、；保4 CCD影像感應n以及其類似物之成 200914254 像元件之光電表面的蓋板，且由諸如BK7之光學玻璃製成。此光學系統單元之透鏡資料展示於下表中。資料展示當由下式表示非球形表面時之值： Z= [(Y2/R)/ {1 +V( 1 -K(Y2/R2))} ]+ΣAi，其中： “Z”為在非球形表面上自A點延伸至B點之法線之長度，其中A點距光轴之距離為Y且B點為非球形表面頂點之接觸平面（垂直於光軸之平面）； “Y”為距光轴之距離； “R”為接近光軸之非球形表面之曲率半徑； “K”為偏心率；且 “ Ai”為非球面係數（i = 3至10 )。表3 貫施例1/基本透鏡資料 Si Ri Di Ndj vdj (11) (12)毫米 (13)毫米 (14) (15) 孔徑光闌 0.000 0.05 1 1.000 1.20 1.510 56.2 2 2.208 0.80 3 2.477 0.80 1.654 28.8 4 2.880 1.20 5 0.000 0.30 1.516 64.1 6 0.000 52 1 1.表面編號；12.曲率半徑；13.表面間距；14.折射率； *5.阿貝數。 200914254C i == one of the primary key ends and the side key has energy; =: = the composite material is effectively used as a raw material for the optical lens, and: injection molding or press forming is performed using a mold of a 1 = surface. The combination of the manufactured glue = and the glass lens is effective as a pre-learning component of St. The light unit unit including the optical lens formed by the above is described below. It should be noted that each of the optical system units of the camera optical system 2 of the digital camera in the mobile phone shown in Fig. 2 is incorporated. [Embodiment 1] The fresh 纟 unit shown in Fig. 4! _ is composed of a second lens 5 and a second lens 6 disposed behind the aperture light on the image side, and the lens disposed in the aperture stop 4 is as early as possible. The plane parallel plate 7 is formed. The first lens $ is a return lens made of methacrylate, and both surfaces thereof are f--the lens 6 is a positive lens using the positive refractive power (positive ==: 1) of the present invention. And both surfaces are aspherical. ', ',; 4 CCD image sensing n and its analog 200914254 like the cover of the photoelectric surface of the component, and made of optical glass such as BK7. The lens data for this optical system unit is shown in the table below. The data shows the value when the aspheric surface is represented by the following formula: Z= [(Y2/R)/ {1 +V( 1 -K(Y2/R2))} ]+ΣAi, where: “Z” is in the non- The length of the spherical surface extending from point A to the normal of point B, where the distance of point A from the optical axis is Y and point B is the contact plane of the vertex of the aspherical surface (perpendicular to the plane of the optical axis); "Y" is The distance from the optical axis; "R" is the radius of curvature of the aspherical surface close to the optical axis; "K" is the eccentricity; and "Ai" is the aspherical coefficient (i = 3 to 10). Table 3 Example 1/Basic Lens Information Si Ri Di Ndj vdj (11) (12) mm (13) mm (14) (15) Aperture stop 0.000 0.05 1 1.000 1.20 1.510 56.2 2 2.208 0.80 3 2.477 0.80 1.654 28.8 4 2.880 1.20 5 0.000 0.30 1.516 64.1 6 0.000 52 1 1. Surface number; 12. Radius of curvature; 13. Surface spacing; 14. Refractive index; *5. Abbe number. 200914254

崎 pu.uuC 實施例1/非球面透嬈實料非球面係數表面編號第一表面 ^第二表面第三表面第四表面 Κ -2.309Ε+00 -8.015Ε+00 1.062E+00 h5.086E+00 αΤ~ 0.000Ε+00 Ο.ΟΟΟΕ+ΟΟ -5.287E-02 -6.803E-02 Α4 1.720Ε-01 1.235Ε-01 6.498E-031 1.441E-01 Α5 0.000Ε+00 0.000Ε+00 -8.159E-02 -1.745E-01 Α6 -8.355Ε-02 1.059Ε-01 2.068E-03 2.136E-02 Α7 A 〇— 0.000Ε+00 0.000Ε+00 1.739E-02 4.416E-02 Α8 -5.517Ε-03 -6.398Ε-02 6.027E-03 -1 287E-02 Α9 0.000Ε+00 Ο.ΟΟΟΕ+ΟΟ" -3 771Κ-0λ :5·540Ε-03 2.093Ε-03 Α10 7.834Ε-03 lL483E-02 [3Τ028Ε-05 f 毫米；Fno = 4.0 ; 2ω = 63.6。。Saki pu.uuC Example 1/Aspherical transparent material Aspheric coefficient Surface number First surface ^ Second surface Third surface Fourth surface Κ -2.309Ε+00 -8.015Ε+00 1.062E+00 h5.086E +00 αΤ~ 0.000Ε+00 Ο.ΟΟΟΕ+ΟΟ -5.287E-02 -6.803E-02 Α4 1.720Ε-01 1.235Ε-01 6.498E-031 1.441E-01 Α5 0.000Ε+00 0.000Ε+00 - 8.159E-02 -1.745E-01 Α6 -8.355Ε-02 1.059Ε-01 2.068E-03 2.136E-02 Α7 A 〇— 0.000Ε+00 0.000Ε+00 1.739E-02 4.416E-02 Α8 -5.517 Ε-03 -6.398Ε-02 6.027E-03 -1 287E-02 Α9 0.000Ε+00 Ο.ΟΟΟΕ+ΟΟ" -3 771Κ-0λ :5·540Ε-03 2.093Ε-03 Α10 7.834Ε-03 lL483E- 02 [3Τ028Ε-05 f mm; Fno = 4.0; 2ω = 63.6. .

w 卜 axiir 。在本文中，焦距f為3 77毫 2ω為63.6。。球面像差、散；/數為切，且視場角由折射率為U54之本發明 ^真如目4中所示。當作為第二透鏡6時I 5材料製成的塑膠透鏡因此，整個物品可能S鏡另鏡6之表面製成非球面。由此將各透鏡5以及各透以及各透鏡6之像差充分地減小。圖4中所示’各透鏡5 [實施例2] 。圖5中所示之光學系統單闌4、由第—透鏡1〇、第二文置於影像側之孔徑光 f安置於孔徑光闌4後方之透以及第三錢12組成第—透鏡10以及第三透鏡12 ::兀以及平行板7構成。酯製成之塑膠透鏡，且其兩個^由（例如）甲基丙烯酸鏡11為由本發明之奈料=相為麵面。第二透兩個表面均麵麵。圖^Μ之貞轉透鏡，且其下之光學系統單元之透鏡 53 200914254 zy iz^+pii.aoc 資料展示於下表中。應注意，焦距f為4.80毫米，F數為 3.62，且視場角2ω為68.6°。球面像差、散光以及失真如圖6中所示。表4 實施例2/基本透鏡資料 Si Ri Di Ndj vdj 孔徑光闌 0.000 -0.14 1 1.863 1.00 1.510 56.2 2 15.801 0.82 3 -2.018 0.70 1.654 28.8 4 -8.02 0.10 5 1.720 1.30 1.510 56.2 6 2.923 1.50 7 0.000 0.30 1.516 64.1 8 0.000w 卜 axiir. In this paper, the focal length f is 3 77 mA 2 ω is 63.6. . Spherical aberration, dispersion; / number is cut, and the angle of view is represented by the present invention in which the refractive index is U54. A plastic lens made of I 5 material when used as the second lens 6 Therefore, the entire object may be made aspherical on the surface of the mirror 6 . Thereby, the aberration of each lens 5 and each of the lenses and the respective lenses 6 is sufficiently reduced. Each lens 5 is shown in Fig. 4 [Embodiment 2]. The optical system unit 4 shown in FIG. 5, the aperture lens f disposed on the image side by the second lens 1 〇, the aperture light f disposed on the image side, and the third lens 12 constitute the first lens 10 and The third lens 12 is formed of ::兀 and the parallel plate 7. A plastic lens made of an ester, and two of them, for example, a methacrylic mirror 11 is a surface of the present invention. The second surface is the surface of both surfaces. Figure Μ 贞贞透镜 , , , , 53 53 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 It should be noted that the focal length f is 4.80 mm, the F number is 3.62, and the angle of view 2ω is 68.6°. Spherical aberrations, astigmatism, and distortion are shown in Figure 6. Table 4 Example 2/Basic Lens Information Si Ri Di Ndj vdj Aperture stop 0.000 -0.14 1 1.863 1.00 1.510 56.2 2 15.801 0.82 3 -2.018 0.70 1.654 28.8 4 -8.02 0.10 5 1.720 1.30 1.510 56.2 6 2.923 1.50 7 0.000 0.30 1.516 64.1 8 0.000

C 54 200914254 ^yi^pn.aoc 實施例2/非球面透鏡資料非球面係數表面編號第一表面第二表面第三表面第四表面 Κ 3.108Ε+00 1.000Ε+00 2.766Ε+00 -3.147Ε+00 A3 -3.535Ε-02 3.676Ε-02 -4.015Ε-02 -2.745Ε-01 Α4 1.680Ε-01 -1.430Ε-01 1.117Ε-01 6.303Ε-02 Α5 -5.922Ε-01 2.746Ε-01 -5.812Ε-03 7.489Ε-02 Α6 6.815Ε-01 -2.845Ε-01 -7.842Ε-02 -9.483Ε-03 Α7 -5.819Ε-02 9.326Ε-02 3.283Ε-02 -1.318Ε-02 Α8 -6.017Ε-01 7.131Ε-02 6.560Ε-02 1.616Ε-02 Α9 4.416Ε-01 -6.403Ε-02 2.201Ε-02 1.322Ε-02 Α10 -1.131Ε-01 2.267Ε-03 -4.447Ε-02 -U10E-02 第五表面第六表面 Κ -2.014Ε+01 -8.137Ε+00 A3 -1.392Ε-01 5.578Ε-02 Α4 2.028Ε-03 Γ1.341Ε-01 Α5 1.959Ε-02 6.585Ε-02 Α6 7.535Ε-03 -5.246Ε-03 Α7 -3.232Ε-03 -6.386Ε-03 Α8 -1.275Ε-03 5.592Ε-04 Α9 1.178Ε-03 8.862Ε-04 Α10 -3.107Ε-04 -2.165Ε-04 f = 4·80 宅米；Fno = 3.62 ; 2ω = 68.60。 [實施例3] 圖7中所示之光學系統單元由安置於影像側之孔徑光闌4、由第一透鏡15、第二透鏡16、第三透鏡17以及第四透鏡18組成且安置於孔徑光闌4後方之透鏡單元以及平行板7構成。第一透鏡15為由ΖΕΟΝ公司製造之塑膠材料“ZEONEX 330R”（商標名）製成之塑膠透鏡，且其兩個表面均為非球面。第二透鏡16為由本發明之奈米複合材料製成之負塑膠透鏡，且其兩個表面均為非球面。第三透 55 200914254 分pu.uoc 鏡17以及第四透鏡18均為由ΖΕΟΝ公司製造之塑膠材料 “ZEONEXE48R” （商標名）製成之塑膠透鏡，且其兩個表面分別為非球面。圖7中所示之光學系統單元之透鏡資料展示於下表中。應注意，焦距f為5.87毫米，F數為2.82, 且視場角2ω為62.4°。球面像差、散光以及失真如圖8中所示。表5 實施例3/基;^ 1透鏡資料 Si Ri Di Ndj vdj 孔徑光闌 0.000 -0.10 1 3.064 1.01 1.510 56.2 2 -4.702 0.13 3 12.432 0.61 1.654 28.8 4 2.665 0.99 5 -4.870 1.12 1.531 55.5 6 -1.173 0.13 7 -609.943 0.66 1.531 55.5 8 1.421 0.75 9 0.000 0.30 1.516 64.1 10 0.000 1.36 56 200914254 zvi/Hpn.aoc 實施例3/非球面透鏡資料非球面係數表面編號第一表面弟二表面第三表面第四表面 Κ -1.861Ε+00 4.471Ε+00 -1.325Ε+01 9.057Ε-01 A3 -4.365Ε-04 -5.076Ε-03 -3.086Ε-03 3.217Ε-03 Α4 -8.609Ε-05 -3.838Ε-03 -2.023Ε-02 -3.113Ε-02 Α5 1.802Ε-03 -1.493Ε-02 -7.670Ε-03 3.674Ε-02 Α6 -3.166Ε-04 -5.850Ε-03 1.026Ε-02 -3.198Ε-02 Α7 -7.693Ε-03 -3.227Ε-03 -2.958Ε-02 -6.986Ε-03 Α8 -1.696Ε-02 3.299Ε-03 -2.639Ε-03 1.097Ε-02 Α9 2.130Ε-02 3.460Ε-03 4.009Ε-02 6.420Ε-03 Α10 -8.241Ε-03 -1.979Ε-03 -1.669Ε-02 -3.804Ε-03 第五表面弟六表面第七表面第八表面 Κ 5.453Ε+00 -2.471Ε+00 1.978Ε+01 -5.705Ε+00 A3 -1.694Ε-04 -4.005Ε-04 -2.430Ε-03 -7.442Ε-03 Α4 -2.924Ε-03 -2.871Ε-02 -2.274Ε-02 -6.414Ε-02 Α5 2.266Ε-02 1.151Ε-02 -6.182Ε-03 3.805Ε-02 Α6 5.288Ε-03 -9.754Ε-04 1.984Ε-03 -6.972Ε-03 Α7 -7.692Ε-03 9.663Ε-04 2.017Ε-03 -2.098Ε-03 Α8 -1.967Ε-03 U05E-03 -5.875Ε-04 5.007Ε-04 Α9 3.000Ε-03 5.891Ε-04 -1.030Ε-04 2.400Ε-04 —Α10 -7.503Ε-04 -3.708Ε-04 6.754Ε-05 -6.721Ε-05 f = 5.87 毫米；Fno=2.82 ; 2ω = 62.4。。第一實施例之第二透鏡6、第二實施例之第二透鏡11 以及第三實施例之第二透鏡16分別由本發明之奈米複合材料製成，且其折射率為1.654且阿貝數為28.8。可根據以下方法精製顯示所述光學性質之奈米複合材料。 [製備無機細粒分散液體] (1)氣化錄細粒之組合物氯4用48%氫氧化鈉水溶液中和濃度為50公克/公升之氧氣化#溶液’且藉此獲得水合锆懸浮液體。將此懸浮液體 57 200914254 2yi^4pix.a〇c 過滤且_子交換水洗_餅。以此方式，獲得水合錯滤餅。將此滤餅溶解於作為溶劑之離子交換水中以制:^、 :匕錯2=15質量％之溶液。將所述溶液置“壓ς 中，f在一C下在150大氣壓之麼力下水熱處理24小時。藉此證實形成氧化锆細粒。粒子之折射率為2.^。 (2)製備氧化錯二甲基乙酿胺分散液體將500公克Ν,Ν1-二甲基乙醯胺添加至上述（1)中所衣備之500公克水合錯懸浮液體（濃度：μ質量％)中，且在減壓下將所得混合物濃縮至約5〇〇公克或更少之量，接著進行溶劑取代。添加ν，ν’-二甲基乙醯胺以調節濃度，藉此獲得15質量％之氧化鍅二曱基乙醯胺分散液體。 [合成聚合物] (1)合成熱塑性聚合物製備2.1公克丙烯酸第三丁酯、ο.?〕公克2-溴-2-甲基丙酸第三丁酯、0.46公克溴化銅⑴、0.56公克 N，N，NW，N”,N”-五甲基二伸乙基四胺以及9毫升甲基乙基酮之混合物，且由氮氣取代混合物中之空氣。將混合物於 80。(：之浴溫的油浴中攪拌1小時，且在氮氣流下向其中添加136.2公克笨乙烯。將混合物在油浴中在卯。C之浴温下授拌16小時且將其冷卻至室溫。隨後，將1〇〇毫升乙酸匕酯以及30公克氧化添加至混合物中且攪拌_ 3〇分鐘。將此反應液體過濾且以液滴形式將濾液傳遞至過量甲醇中^ 將所形成之沈澱物用曱醇洗滌且乾燥。藉此獲得61公克聚合物。將此聚合物溶解於300毫升曱苯中，J_向其中添力 58 200914254 zyi^4pn.a〇c 6 t克對甲笨俩水合物且藉由加熱回流3小時。以液滴 5 = ί應液體傳遞至過量甲醇中。將所形成之沈殺物妙rpi〜且乾燦。藉此獲得55》克鼓段共聚物Q·1。根據刀析儀之量測，此聚合物之數量平均分子量為 32000且重量平诒八工旦达1 J刀丁里為、目丨丨夕+取yw勾刀子里為35000。另外，由阿貝折射計量 /貝J之此I合物之折射率為159。有機-無機奈米複合物以及製造透明模製產品 C透鏡基底材料）] 性聚合物Μ、間聯三苯以及表面修飾劑“ _ =1添加至氧化#二？基乙㈣分散液體中以使得 2固體含量/ΙΜ/間聯三笨/a-萘基乙酸之重量比變為 4下1力7ΓΓ曲·2/8·3,且藉由翻吏其均—混合。藉由在= 下加…、來辰縮二甲基乙酿胺溶液。藉由表面由sus製成之权具對濃縮殘餘物進行熱壓縮（溫度：180。〇，壓力：137 兆帕斯卡，時間：2分鐘）。藉 ' 產品（透鏡基底材料） "^厂子度為U米之模製貫施例中所示，根據本發明之光學透鏡用作在構成先學錢單蚊親巾具有最高折料之透鏡。因為具有低折射率之習知瓣透鏡可用作其他透鏡，所以可降低光學系統單元之生產成本。在上述實施例1至3中，用於保護各成像元件之光電表面的蓋板為不具有光焦度 (optical (refractive) p〇wer)之玻璃透鏡。然而，由本發月之者米複合材料製成之光學透鏡可與具有（例如）正或負光'、、、度之玻璃透鏡（球面以及非球面透鏡均可應用）組 59 200914254 2yi^4pu.aoc 合此外’與用於光學透鏡之習知塑膠材料相比，之奈米複合材料具有較南折射率以及較高分散性。學透鏡令有效應用所述光學性質，將本發明之夺米禮人料用於具有低光焦度之正或負透鏡，因此使色像差以曲率降低。此時，較佳滿足下列條件等式：豕 4xf>fp， Γ 其中％”為光學透鏡之焦距且“f，，為句，個系統的焦距。此外，由於環境溫為度本發Γ奈米複合材料降低折射;' =兀之塑膠透鏡中安置於溫度最寬泛改變處之時，、物'^之溫度性質得以改良。吋 :管^述實施例中所述之光學系統單二的攝影光學系統：2 可用於其他目的。舉例而言，當透鏡 ^足必要光學條件時，本發 7又 :影元件，其中液晶面板用作影像早::應用於于系統單元亦可應用各種光發明之光距裴置之井學旦、al 予凡件（堵如干涉儀/光學測予里氣件）之光學系統。 L圖式簡單說明】細二====:=«中時無機圖2熹且士于、巧卞、间的相互關係的圖。疋具有内建式數位攝影機之行動電話的外部圖。 60 200914254C 54 200914254 ^yi^pn.aoc Example 2/Aspheric lens data Aspheric coefficient surface number First surface Second surface Third surface Fourth surface Κ 3.108Ε+00 1.000Ε+00 2.766Ε+00 -3.147Ε +00 A3 -3.535Ε-02 3.676Ε-02 -4.015Ε-02 -2.745Ε-01 Α4 1.680Ε-01 -1.430Ε-01 1.117Ε-01 6.303Ε-02 Α5 -5.922Ε-01 2.746Ε-01 -5.812Ε-03 7.489Ε-02 Α6 6.815Ε-01 -2.845Ε-01 -7.842Ε-02 -9.483Ε-03 Α7 -5.819Ε-02 9.326Ε-02 3.283Ε-02 -1.318Ε-02 Α8 - 6.017Ε-01 7.131Ε-02 6.560Ε-02 1.616Ε-02 Α9 4.416Ε-01 -6.403Ε-02 2.201Ε-02 1.322Ε-02 Α10 -1.131Ε-01 2.267Ε-03 -4.447Ε-02 - U10E-02 Fifth surface sixth surface Κ -2.014Ε+01 -8.137Ε+00 A3 -1.392Ε-01 5.578Ε-02 Α4 2.028Ε-03 Γ1.341Ε-01 Α5 1.959Ε-02 6.585Ε-02 Α6 7.535Ε-03 -5.246Ε-03 Α7 -3.232Ε-03 -6.386Ε-03 Α8 -1.275Ε-03 5.592Ε-04 Α9 1.178Ε-03 8.862Ε-04 Α10 -3.107Ε-04 -2.165Ε-04 f = 4·80 house rice; Fno = 3.62; 2ω = 68.60. [Embodiment 3] The optical system unit shown in Fig. 7 is composed of an aperture stop 4 disposed on the image side, composed of a first lens 15, a second lens 16, a third lens 17, and a fourth lens 18 and disposed in the aperture The lens unit behind the aperture 4 and the parallel plate 7 are formed. The first lens 15 is a plastic lens made of a plastic material "ZEONEX 330R" (trade name) manufactured by Azbil Corporation, and both surfaces thereof are aspherical. The second lens 16 is a negative plastic lens made of the nanocomposite of the present invention, and both surfaces thereof are aspherical. The third permeable 55 200914254 pu.uoc mirror 17 and the fourth lens 18 are plastic lenses made of plastic material "ZEONEXE48R" (trade name) manufactured by the company, and the two surfaces thereof are aspherical. The lens data for the optical system unit shown in Figure 7 is shown in the table below. It should be noted that the focal length f is 5.87 mm, the F number is 2.82, and the angle of view 2ω is 62.4°. Spherical aberrations, astigmatism, and distortion are shown in Figure 8. Table 5 Example 3/base; ^ 1 lens data Si Ri Di Ndj vdj aperture stop 0.000 -0.10 1 3.064 1.01 1.510 56.2 2 -4.702 0.13 3 12.432 0.61 1.654 28.8 4 2.665 0.99 5 -4.870 1.12 1.531 55.5 6 -1.173 0.13 7 - 609.943 0.66 1.531 55.5 8 1.421 0.75 9 0.000 0.30 1.516 64.1 10 0.000 1.36 56 200914254 zvi/Hpn.aoc Example 3/Aspheric lens data Aspheric coefficient surface number First surface Diji Second surface Third surface Fourth surface Κ -1.861Ε+00 4.471Ε+00 -1.325Ε+01 9.057Ε-01 A3 -4.365Ε-04 -5.076Ε-03 -3.086Ε-03 3.217Ε-03 Α4 -8.609Ε-05 -3.838Ε-03 - 2.023Ε-02 -3.113Ε-02 Α5 1.802Ε-03 -1.493Ε-02 -7.670Ε-03 3.674Ε-02 Α6 -3.166Ε-04 -5.850Ε-03 1.026Ε-02 -3.198Ε-02 Α7 - 7.693Ε-03 -3.227Ε-03 -2.958Ε-02 -6.986Ε-03 Α8 -1.696Ε-02 3.299Ε-03 -2.639Ε-03 1.097Ε-02 Α9 2.130Ε-02 3.460Ε-03 4.009Ε- 02 6.420Ε-03 Α10 -8.241Ε-03 -1.979Ε-03 -1.669Ε-02 -3.804Ε-03 The fifth surface of the sixth surface of the seventh surface of the eighth surface Κ 5.453Ε+00 -2.471Ε+00 1.978Ε +01 -5.705Ε+00 A3 -1.694Ε-04 -4.005Ε-04 -2.430Ε-03 -7.442Ε-03 Α4 -2.924Ε-03 -2.871Ε-02 -2.274Ε-02 -6.414Ε-02 Α5 2.266Ε-02 1.151Ε- 02 -6.182Ε-03 3.805Ε-02 Α6 5.288Ε-03 -9.754Ε-04 1.984Ε-03 -6.972Ε-03 Α7 -7.692Ε-03 9.663Ε-04 2.017Ε-03 -2.098Ε-03 Α8 - 1.967Ε-03 U05E-03 -5.875Ε-04 5.007Ε-04 Α9 3.000Ε-03 5.891Ε-04 -1.030Ε-04 2.400Ε-04 —Α10 -7.503Ε-04 -3.708Ε-04 6.754Ε-05 -6.721Ε-05 f = 5.87 mm; Fno=2.82 ; 2ω = 62.4. . The second lens 6 of the first embodiment, the second lens 11 of the second embodiment, and the second lens 16 of the third embodiment are respectively made of the nano composite material of the present invention, and have a refractive index of 1.654 and an Abbe number. It is 28.8. The nano composite material exhibiting the optical properties can be refined according to the following method. [Preparation of inorganic fine particle dispersion liquid] (1) Composition of gasification recording fine particle chlorine 4 was neutralized with a 48% aqueous sodium hydroxide solution to a concentration of 50 g/liter of oxygenated #solution' and thereby obtained a hydrated zirconium suspension liquid . The suspension liquid 57 200914254 2yi^4pix.a〇c was filtered and the _sub-exchanged water-washed cake. In this way, a hydrated filter cake is obtained. This cake was dissolved in ion-exchanged water as a solvent to prepare a solution of 2: 15% by mass. The solution was placed in a "compression crucible, and f was hydrothermally treated at 150 C for 24 hours under a pressure of 150 atm. This confirmed the formation of zirconia fine particles. The refractive index of the particles was 2.^. (2) Preparation of oxidation error Dimethyl ethoxylated amine dispersion liquid 500 g of hydrazine, decyl 1-dimethylacetamide was added to 500 g of the hydrated hydrolytic suspension liquid (concentration: μ mass%) prepared in the above (1), and was reduced The resulting mixture was concentrated to about 5 gram or less by pressure, followed by solvent substitution. ν, ν'-dimethylacetamide was added to adjust the concentration, thereby obtaining 15% by mass of cerium oxide di Ethyl amide dispersion liquid [Synthetic polymer] (1) Synthesis of thermoplastic polymer Preparation of 2.1 g of tert-butyl acrylate, ο.?] g of 2-bromo-2-methylpropionic acid tert-butyl ester, 0.46 g a mixture of copper (1) bromide (1), 0.56 g of N,N,NW,N",N"-pentamethyldiethylidenetetraamine and 9 ml of methyl ethyl ketone, and the mixture of nitrogen in the mixture is replaced by nitrogen. Stir in an oil bath of 80 ° (bath) for 1 hour, and add 136.2 g of stupid ethylene to it under a nitrogen stream. The mixture was stirred in an oil bath at a bath temperature of 卯C for 16 hours and cooled to room temperature. Subsequently, 1 liter of decyl acetate and 30 gram of oxidation were added to the mixture and stirred for _ 3 Torr. The reaction liquid was filtered and the filtrate was transferred to excess methanol in the form of droplets. The formed precipitate was washed with decyl alcohol and dried, thereby obtaining 61 gram of polymer. This polymer was dissolved in 300 ml of benzene. In the middle, J_ adds 58 to it. 200914254 zyi^4pn.a〇c 6 t gram of hydrated hydrate and is refluxed by heating for 3 hours. The liquid is transferred to excess methanol by droplets 5 = ί. The formation of the sinking material is wonderful rpi~ and dry, thereby obtaining 55" gram drum copolymer Q·1. According to the measurement of the knife analyzer, the number average molecular weight of the polymer is 32000 and the weight is flat. Up to 1 J knives, and yaw yw knives are 35000. In addition, the refractive index of the I compound is 159. The organic-inorganic nanocomposite and Manufacture of transparent molded products C lens base material)] Polymer Μ, meta-triphenyl and surface modifier " _ =1 added to oxidation #二? The base (4) is dispersed in the liquid such that the weight ratio of the solid content / ΙΜ / 间三笨 / a - naphthyl acetic acid becomes 4 times 1 force 7 · · 2 / 8 · 3, and by turning over the 均 - mixing. By adding ...... under the =, dimethyl acetamide solution. The concentrated residue was heat-compressed by a device made of sus on the surface (temperature: 180 Torr, pressure: 137 MPa, time: 2 minutes). By the 'product (lens base material) "^the factory degree is U-mold. As shown in the example, the optical lens according to the present invention is used as a lens having the highest folding material in the composition of the first-person mosquito. Since a conventional valve lens having a low refractive index can be used as the other lens, the production cost of the optical system unit can be reduced. In the above-described Embodiments 1 to 3, the cover for protecting the photoelectric surface of each of the imaging elements is a glass lens having no optical (refractive). However, an optical lens made of this moon's rice composite material can be combined with a glass lens (for both spherical and aspherical lenses) having (for example) positive or negative light, and degrees 59 200914254 2yi^4pu. Aoc In addition, the nanocomposite has a souther refractive index and a higher dispersibility than conventional plastic materials for optical lenses. The lens is used to effectively apply the optical properties, and the present invention is used for a positive or negative lens having a low power, thereby reducing chromatic aberration with curvature. At this time, it is preferable to satisfy the following conditional equation: 豕 4xf > fp, Γ where %" is the focal length of the optical lens and "f," is the focal length of the system. In addition, due to the ambient temperature, the hairpin nanocomposite reduces the refraction; when the plastic lens in the '=兀 is placed at the widest temperature change, the temperature property of the object is improved.吋 : The photographic optical system of the optical system described in the embodiment: 2 can be used for other purposes. For example, when the lens is necessary for optical conditions, the present invention is also a shadow element, wherein the liquid crystal panel is used as an image early:: applied to the system unit, and can also be applied to various optical inventions. , al to the optical system of the piece (blocking the interferometer / optical measurement of the gas). A simple description of the L pattern] Fine 2 ====:=«Intra-inorganic Figure 2 is a diagram of the relationship between Yu Shi, Qiao Yu, and between. External diagram of a mobile phone with a built-in digital camera. 60 200914254

z^iZH-pn.auC 圖3是根據本發明之第一實施例之透鏡的方塊圖。圖4是第一實施例之像差圖。圖5是根據本發明之第二實施例之透鏡的方塊圖。圖6是第二實施例之像差圖。圖7是根據本發明之第三實施例之透鏡的方塊圖。圖8是第三實施例之像差圖。【主要元件符號說明】z^iZH-pn.auC Fig. 3 is a block diagram of a lens according to a first embodiment of the present invention. Fig. 4 is an aberration diagram of the first embodiment. Figure 5 is a block diagram of a lens in accordance with a second embodiment of the present invention. Fig. 6 is an aberration diagram of the second embodiment. Figure 7 is a block diagram of a lens in accordance with a third embodiment of the present invention. Fig. 8 is an aberration diagram of the third embodiment. [Main component symbol description]

2:攝影光學系統 4 :孔徑光闌 5 :第一透鏡 6 :第二透鏡 7 :平面平行板/平行板 10 第一透鏡 11 第二透鏡 12 第三透鏡 15 第一透鏡 16 第二透鏡 17 第三透鏡 18 第四透鏡 612: Photographic optical system 4: aperture stop 5: first lens 6: second lens 7: plane parallel plate/parallel plate 10 first lens 11 second lens 12 third lens 15 first lens 16 second lens 17 Three lens 18 fourth lens 61

Claims

200914254 2yi24pit.doc 十、申請專利範圍： 1.一種光學透鏡，其包含： 2·無機混合材料，其含有無機細粒以及熱塑性聚合中所述熱塑性聚合物在主鏈末端以及侧鏈之至少— 基，且所述官能基與所述無機細粒之至少- 光學====所料學賴，其中所述光學範圍第1項所述之光學透鏡，其中所述尤予透鏡為正非球面透鏡或負非球面透鏡。 4.種光學糸統單元，其包含：折射，/中在所述塑膠透鏡中具有最大述有機-無機混合材料含；I 成之7^予透鏡，所中所述埶塑及熱塑性聚合物，其化=基，且所述宫能基舆所述無機細教之至少一^成 5.種光學系統單元，其包含：至少兩個塑膠透鏡，苴巾處的透鏡為由有機-無機混人I置制於:度/4b最廣之位置述熱塑性聚合物在主m 及熱塑性聚合物，其中所 :基’且所述官能基與所述無機細粒之至少一= 62 200914254 zy 丄 24pii.aoc 6. 如申請專利範圍第4項所述之光學系統單元，更包括至少一個玻璃透鏡。 7. —種光學元件，其包含：由有機-無機混合材料製成之光學透鏡，所述有機-無機混合材料含有無機細粒以及熱塑性聚合物，其中所述熱塑性聚合物在主鏈末端以及侧鏈之至少一者中具有官能基，且所述官能基與所述無機細粒之至少一者形成化學鍵，或者包括所述光學透鏡之光學系統單元。 8. 如申請專利範圍第7項所述之光學元件，其中所述光學元件為成像元件。 9. 如申請專利範圍第7項所述之光學元件，其中所述光學元件為投影元件。 10. 如申請專利範圍第7項所述之光學元件，其中所述光學元件為光學量測元件。200914254 2yi24pit.doc X. Patent application scope: 1. An optical lens comprising: 2. an inorganic mixed material containing inorganic fine particles and a thermoplastic polymer at least at the end of the main chain and at the side chain And the optical lens of the optical range of claim 1, wherein the eutectic lens is a positive aspheric lens. Or a negative aspherical lens. 4. An optical unit comprising: a refractive index, wherein the plastic lens has a maximum of the organic-inorganic hybrid material; and the lens is a lens, wherein the plastic and thermoplastic polymer are And an optical system unit comprising: at least two plastic lenses, the lens at the wipe is made of an organic-inorganic hybrid I The thermoplastic polymer is in the main m and the thermoplastic polymer, wherein: the base ' and at least one of the functional group and the inorganic fine particle = 62 200914254 zy 丄 24pii.aoc 6. The optical system unit of claim 4, further comprising at least one glass lens. 7. An optical element comprising: an optical lens made of an organic-inorganic hybrid material comprising inorganic fine particles and a thermoplastic polymer, wherein the thermoplastic polymer is at the end of the main chain and at the side At least one of the chains has a functional group, and the functional group forms a chemical bond with at least one of the inorganic fine particles or an optical system unit of the optical lens. 8. The optical component of claim 7, wherein the optical component is an imaging component. 9. The optical component of claim 7, wherein the optical component is a projection component. 10. The optical component of claim 7, wherein the optical component is an optical measurement component.