JP2009227836A - Organic-inorganic composite composition, method of manufacturing molded article, and optical component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite composition that has a high light transmittance and a high refractive index and remains on a mold after molded in a suppressed amount. <P>SOLUTION: The organic-inorganic composite composition includes a thermoplastic resin, bearing a functional group can form an optional chemical bond with an inorganic fine particle at an end or in a side chain of the polymer, and an inorganic fine particle and satisfies equation (1) [wherein γ<SB>s</SB><SP>p</SP>(mN/m) is a polar component of a surface free energy of the composition measured at 25°C and a relative humidity of 60%; and E (J/m<SP>2</SP>) is a fracture energy density of the composition]. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic-inorganic composite composition having a high light transmittance and a refractive index, and a reduced amount of mold remaining after molding, and a lens substrate (for example, a spectacle lens, an optical lens) comprising the same. The present invention relates to optical components such as equipment lenses, optoelectronic lenses, laser lenses, pickup lenses, in-vehicle camera lenses, portable camera lenses, digital camera lenses, OHP lenses, and the like.

  In recent years, research on optical materials has been actively conducted, and particularly in the field of lens materials, development of materials excellent in high refraction, transparency, lightness, easy moldability, releasability, etc. is strongly desired. Yes.

  Plastic lenses are lighter and harder to break than inorganic materials such as glass and can be processed into various shapes, so in recent years they are rapidly spreading not only to spectacle lenses but also to optical materials such as portable camera lenses and pickup lenses. .

  Along with this, it has been required to increase the refractive index of the material itself in order to reduce the thickness of the lens. For example, a technique for introducing a sulfur atom into a polymer (see Patent Document 1 and Patent Document 2) In addition, a technique for introducing a halogen atom or an aromatic ring into a polymer (see Patent Document 3), a technique using a copolymer of an indene derivative and a vinyl monomer (see Patent Document 4), and the like have been actively studied. . However, a plastic material that has a sufficiently large refractive index and has good transparency and can be used as a substitute for glass has not yet been developed.

  Since it is difficult to increase the refractive index with only an organic substance, attempts have been made to produce a high refractive index material by dispersing an inorganic substance having a high refractive index in a resin matrix (see Patent Documents 5 and 6). In order to reduce attenuation of transmitted light due to Rayleigh scattering, it is preferable to uniformly disperse inorganic fine particles having a particle diameter of 15 nm or less in the resin matrix. However, since primary particles having a particle diameter of 15 nm or less are very likely to aggregate, it is extremely difficult to uniformly disperse them in the resin matrix. In addition, when the attenuation of transmitted light in the optical path length corresponding to the lens thickness is taken into consideration, the amount of inorganic fine particles added must be limited. For this reason, it has been required to disperse the fine particles in the resin matrix at a high concentration without reducing the transparency of the resin.

In order to meet such a demand, an organic-inorganic composite composition in which inorganic fine particles are dispersed in a thermoplastic resin having a functional group capable of forming a chemical bond with inorganic fine particles has been proposed (see Patent Document 7). This organic-inorganic composite composition has a good dispersibility of the inorganic fine particles and achieves a refractive index of 1.60 or more.
JP 2002-131502 A Japanese Patent Laid-Open No. 10-298287 JP 2004-244444 A JP 2001-89537 A JP 61-291650 A JP 2003-73564 A JP 2007-238929 A

However, when an optical lens is produced using the organic-inorganic composite composition described in Patent Document 7, there is a problem that the organic-inorganic composite composition may remain in the mold after molding. Became clearer.
The present invention has been made in view of the above circumstances, and the object thereof is an organic-inorganic composite composition having a high light transmittance and a refractive index, and a reduced residual mold after molding, and the organic-inorganic composite The object is to provide a simple molding method using the composition.

  As a result of intensive investigations to achieve the above object, the present inventors have found that an organic-inorganic composite composition containing a thermoplastic resin having a specific functional group and inorganic fine particles and satisfying a specific condition is highly refractive. It was found that the remaining amount of the mold after molding was suppressed while having excellent transparency, and the present invention described below was completed.

［上式において、γ_s ^pは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物の表面自由エネルギーの極性成分（ｍＮ／ｍ）であり、Ｅは前記有機無機複合組成物の破断エネルギー密度（Ｊ／ｍ²）である。］
［２］
前記破断エネルギー密度が３０．０Ｊ／ｍ²以上であるであることを特徴とする、［１］に記載の有機無機複合組成物複合組成物。
［３］ 前記熱可塑性樹脂が、８５℃以上のガラス転移温度を有することを特徴とする、［１］または［２］に記載の有機無機複合組成物。
［４］ 前記熱可塑性樹脂が、

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基を有することを特徴とする、［１］〜［３］のいずれか一項に記載の有機無機複合組成物。
［５］ 前記熱可塑性樹脂が、前記官能基を高分子鎖１本あたり平均０.１〜２０個有していることを特徴とする［１］〜［４］のいずれか一項に記載の有機無機複合組成物。
［６］ 前記熱可塑性樹脂が、スチレンまたはスチレン誘導体を重合することにより形成される単位構造を少なくとも一つ有することを特徴とする、［１］〜［５］のいずれか一項に記載の有機無機複合組成物。
［７］ 前記熱可塑性樹脂が、下記一般式（２１）〜（２３）のいずれかで表される単位構造を少なくとも一種有することを特徴とする、［１］〜［６］のいずれか一項に記載の有機無機複合組成物。

［ 一般式（２１）中、Ｒ¹はアルキル基、パーフルオロアルキル基またはアリール基を表し、ｎは５以上の整数を表す。］

［一般式（２２）中、ｍは１以上の整数を表す。］

［一般式（２３）中、ｑは４以上の整数を表す。］
［８］ 前記熱可塑性樹脂が下記一般式（４）で表される単位構造を有することを特徴とする、［１］〜［７］のいずれか一項に記載の有機無機複合組成物。

［一般式（４）中、Ｒ³は水素原子またはメチル基を表し、Ｒ⁴はメチル基またはフェニル基を表し、Ｒ⁵は水素原子またはアルキル基を表し、Ｘはアルキレン基またはアリーレン基からなる二価の連結基を表し、ｎは５以上の整数を表す。］
［９］ 前記熱可塑性樹脂が下記一般式（５）で表される単位構造を少なくとも一つ有することを特徴とする、［１］〜［８］のいずれか一項に記載の有機無機複合組成物。

［一般式（５）中、Ｘは水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表す。］
［１０］ 前記無機微粒子の粒子サイズが１〜３０ｎｍであることを特徴とする、［１］〜［９］のいずれか一項に記載の有機無機複合組成物。
［１１］ 前記無機微粒子を２０質量％以上含むことを特徴とする、［１］〜［１０］のいずれか一項に記載の有機無機複合組成物。
［１２］ 厚さ１ｍｍ換算の光線透過率が波長５８９ｎｍにおいて７０％以上であることを特徴とする、［１］〜［１１］のいずれか一項に記載の有機無機複合組成物。
［１３］ 波長５８９ｎｍにおける屈折率が１．６０以上であることを特徴とする、［１］〜［１２］のいずれか一項に記載の有機無機複合組成物。
［１４］ 前記無機微粒子が、酸化ジルコニウム、酸化亜鉛、酸化錫および酸化チタンからなる群より選ばれるいずれか一つであることを特徴とする、［１］〜［１３］のいずれか一項に記載の有機無機複合組成物。 [1]
An organic-inorganic composite composition comprising a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain, and inorganic fine particles, and satisfying the following formula (1): .

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), E is the organic-inorganic composite It is the breaking energy density (J / m ² ) of the composition. ]
[2]
The organic-inorganic composite composition composite composition according to [1], wherein the breaking energy density is 30.0 J / m ² or more.
[3] The organic-inorganic composite composition according to [1] or [2], wherein the thermoplastic resin has a glass transition temperature of 85 ° C. or higher.
[4] The thermoplastic resin is

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. The organic-inorganic composite composition according to any one of [1] to [3], which has one or more functional groups selected from the group consisting of:
[5] The thermoplastic resin according to any one of [1] to [4], wherein the thermoplastic resin has an average of 0.1 to 20 functional groups per polymer chain. Organic inorganic composite composition.
[6] The organic material according to any one of [1] to [5], wherein the thermoplastic resin has at least one unit structure formed by polymerizing styrene or a styrene derivative. Inorganic composite composition.
[7] Any one of [1] to [6], wherein the thermoplastic resin has at least one unit structure represented by any one of the following general formulas (21) to (23). The organic-inorganic composite composition described in 1.

[In General Formula (21), R ¹ represents an alkyl group, a perfluoroalkyl group or an aryl group, and n represents an integer of 5 or more. ]

[In General Formula (22), m represents an integer of 1 or more. ]

[In General Formula (23), q represents an integer of 4 or more. ]
[8] The organic-inorganic composite composition according to any one of [1] to [7], wherein the thermoplastic resin has a unit structure represented by the following general formula (4).

[In General Formula (4), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a methyl group or a phenyl group, R ⁵ represents a hydrogen atom or an alkyl group, and X consists of an alkylene group or an arylene group. Represents a divalent linking group, and n represents an integer of 5 or more. ]
[9] The organic-inorganic composite composition according to any one of [1] to [8], wherein the thermoplastic resin has at least one unit structure represented by the following general formula (5). object.

[In General Formula (5), X represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]
[10] The organic-inorganic composite composition according to any one of [1] to [9], wherein the inorganic fine particles have a particle size of 1 to 30 nm.
[11] The organic-inorganic composite composition according to any one of [1] to [10], wherein the inorganic fine particles are contained in an amount of 20% by mass or more.
[12] The organic-inorganic composite composition according to any one of [1] to [11], wherein the light transmittance in terms of thickness of 1 mm is 70% or more at a wavelength of 589 nm.
[13] The organic-inorganic composite composition according to any one of [1] to [12], wherein a refractive index at a wavelength of 589 nm is 1.60 or more.
[14] The inorganic particles are any one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide, and titanium oxide, according to any one of [1] to [13] The organic-inorganic composite composition described.

［上式において、γ_s ^pは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物の表面自由エネルギーの極性成分（ｍＮ／ｍ）であり、αは前記有機無機複合組成物の２５℃〜５０℃の平均線膨張係数（／Ｋ）であり、Ｅは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物のヤング率（Ｎ／ｍ²）である。］
［１９］ 有機無機複合組成物を溶融して金型内に充填し、充填した有機無機複合組成物を固化した後に前記金型から成型品を取り出したときの、前記有機無機複合組成物の金型残存量を抑える方法であって、
前記有機無機複合組成物として、高分子末端または側鎖に無機微粒子と任意の化学結合を形成しうる官能基を有する熱可塑性樹脂と無機微粒子を含有し、かつ下記式（１）を満たす有機無機複合組成物を選択することを特徴とする、金型から成型品を取り出した後の有機無機複合組成物の金型残存量を抑える方法。

［上式において、γ_s ^pは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物の表面自由エネルギーの極性成分（ｍＮ／ｍ）であり、αは前記有機無機複合組成物の２５℃〜５０℃の平均線膨張係数（／Ｋ）であり、Ｅは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物のヤング率（Ｎ／ｍ²）である。］ [15] The organic-inorganic composite composition according to any one of [1] to [14] is melted and filled in a mold, and the filled organic-inorganic composite composition is solidified and then molded from the mold. A method for producing a molded product, wherein the product is taken out.
[16] The die according to [15], wherein the mold contains at least one element selected from the group consisting of iron, copper, zinc, nickel, chromium, molybdenum, vanadium, and tungsten. Method of manufacturing molded products.
[17] The method for producing a molded article according to [15] or [16], wherein the molten organic-inorganic composite composition is directly filled into a mold.
[18] An organic-inorganic composite composition containing a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain and inorganic fine particles and satisfying the following formula (1) is selected. A method for selecting an organic-inorganic composite composition that does not remain in a mold when released from the mold.

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), α is the organic-inorganic composite E is the Young's modulus (N / m ² ) of the organic-inorganic composite composition measured at 25 ° C. and 60% relative humidity. ). ]
[19] The metal of the organic-inorganic composite composition when the organic-inorganic composite composition is melted and filled into a mold, and the molded product is taken out from the mold after the filled organic-inorganic composite composition is solidified. A method for reducing the residual amount of a mold,
As the organic-inorganic composite composition, an organic / inorganic material containing a thermoplastic resin having inorganic fine particles and a functional group capable of forming an arbitrary chemical bond at the polymer terminal or side chain and inorganic fine particles and satisfying the following formula (1) A method for suppressing a residual amount of a mold of an organic-inorganic composite composition after taking out a molded product from the mold, wherein the composite composition is selected.

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), α is the organic-inorganic composite E is the Young's modulus (N / m ² ) of the organic-inorganic composite composition measured at 25 ° C. and 60% relative humidity. ). ]

[20] An optical component comprising the organic-inorganic composite composition according to any one of [1] to [14].
[21] The optical component according to [20], wherein the optical component is a lens.

  The organic-inorganic composite composition of the present invention has high light transmittance and refractive index, and the residual amount of the mold after molding is suppressed. Moreover, according to the molding method of the present invention, a molded body can be produced by a simple method. Furthermore, the optical component of the present invention has excellent transparency and a high refractive index.

  Hereinafter, the organic-inorganic composite composition of the present invention and its utilization form will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Thermoplastic resin]
The thermoplastic resin used in the present invention is a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain.

  The basic structure of the thermoplastic resin used in the present invention is not particularly limited. For example, poly (meth) acrylate, polystyrene, polyamide, polyvinyl ether, polyvinyl ester, polyvinyl carbazole, polyolefin, polyester, polycarbonate, polyurethane, poly Examples thereof include resins having a known structure such as thiourethane, polyimide, polyether, polythioate, polyetherketone, polysulfone, and polyethersulfone.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基 It is preferable to select any of the following thermoplastic resins (1) to (3) as a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer chain terminal or side chain.
Thermoplastic resin (1): a thermoplastic resin having a functional group selected from the following in the side chain

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. One or more functional groups selected from the group consisting of

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基 Thermoplastic resin (2): a thermoplastic resin having a functional group selected from the following at least at one position of the polymer terminal

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. One or more functional groups selected from the group consisting of

Thermoplastic resin (3): a block copolymer composed of a hydrophobic segment and a hydrophilic segment;

  Hereinafter, these thermoplastic resins (1) to (3) will be described in detail.

Thermoplastic resin (1)
The thermoplastic resin (1) used in the present invention has a functional group capable of forming a chemical bond with inorganic fine particles in the side chain. Here, the “chemical bond” includes, for example, a covalent bond, an ionic bond, a coordination bond, a hydrogen bond, and the like, and when there are a plurality of functional groups, each can form a chemical bond different from the inorganic fine particles. It may be. Whether or not a chemical bond can be formed is determined by whether or not the functional group of the thermoplastic resin can form a chemical bond with the inorganic fine particle when the thermoplastic resin and the inorganic fine particle are mixed in an organic solvent. All of the functional groups of the thermoplastic resin may form chemical bonds with the inorganic fine particles, or some of them may form chemical bonds with the inorganic fine particles.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基である。 The functional group capable of binding to the inorganic fine particles has a function of stably dispersing the inorganic fine particles in the thermoplastic resin by forming a chemical bond with the inorganic fine particles. Functional groups that can form chemical bonds with inorganic fine particles

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. ] One or more functional groups selected from the group consisting of

The preferred ranges of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are the following ranges.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group. Substituted alkyl groups include, for example, aralkyl groups. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group. The aryl group preferably has 6 to 30 carbon atoms, more preferably 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 herein includes a heteroaryl group. As substituents for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, in addition to these alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) And alkoxy groups (for example, methoxy group, ethoxy group). R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
Preferable ranges of R ¹⁷ and R ¹⁸ are the same as those of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ . n is preferably 3.

、−ＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1であり、より好ましくは、

または−ＣＯ₂Ｈまたはその塩である。 Among these functional groups, preferably

, -SO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -Si a ^{_{(OR 15) m1 R 16 3}} -m1, more preferably,

Or —CO ₂ H or a salt thereof.

  The thermoplastic resin used in the present invention is particularly preferably a copolymer having a repeating unit represented by the following general formula (11). Such a copolymer can be obtained by copolymerizing a vinyl monomer represented by the following general formula (12).

In general formula (11) and general formula (12), R represents a hydrogen atom, a halogen atom or a methyl group, and X represents —CO ₂ —, —OCO—, —CONH—, —OCONH—, —OCOO—, It represents a divalent linking group selected from the group consisting of —O—, —S—, —NH—, and a substituted or unsubstituted arylene group, more preferably —CO ₂ — or a p-phenylene group.

  Y represents a divalent linking group having 1 to 30 carbon atoms. 1-20 are preferable, as for carbon number, 2-10 are more preferable, and 2-5 are more preferable. Specific examples include an alkylene group, an alkyleneoxy group, an alkyleneoxycarbonyl group, an arylene group, an aryleneoxy group, an aryleneoxycarbonyl group, and a combination thereof, and an alkylene group is preferable.

  q represents the integer of 0-18. More preferably, it is an integer of 0-10, More preferably, it is an integer of 0-5, Most preferably, it is an integer of 0-1.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基を表し、好ましくは

であり、さらに好ましくは、

である。 Z is

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. Represents one or more functional groups selected from the group consisting of

And more preferably

It is.

Here, the definitions and specific examples of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and n are each independently the above-mentioned R ¹¹ , R ¹² , R ¹³ , ^{R 14, R 15, R 16} , R 17, the same meanings as defined and specific examples of R ¹⁸ and n. However, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and n are each preferably a hydrogen atom or an alkyl group.

  Specific examples of the monomer represented by the general formula (12) are given below, but the monomer that can be used in the present invention is not limited thereto.

［ 一般式（２１）中、Ｒ¹はアルキル基、パーフルオロアルキル基またはアリール基を表し、ｎは５以上の整数を表す。］

［一般式（２２）中、ｍは１以上の整数を表す。］

［一般式（２３）中、ｑは４以上の整数を表す。］ The thermoplastic resin used in the present invention preferably has at least one unit structure represented by any one of the following general formulas (21) to (23) from the viewpoint of surface free energy.

[In General Formula (21), R ¹ represents an alkyl group, a perfluoroalkyl group or an aryl group, and n represents an integer of 5 or more. ]

[In General Formula (22), m represents an integer of 1 or more. ]

[In General Formula (23), q represents an integer of 4 or more. ]

  Specific examples of the monomer having at least one unit structure represented by any one of the general formulas (21) to (23) are given below as S-1 to S-35, and the monomers that can be employed in the present invention Is not limited to these specific examples.

［一般式（２５）中、Ｘは水素原子、置換もしくは無置換のアルキル基、または置換もしくは無置換のアリール基を表す。］ The thermoplastic resin used in the present invention preferably has at least one unit structure represented by the following general formula (25) from the viewpoint of toughness.

[In General Formula (25), X represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]

  Specific examples of the monomer having a unit structure represented by the following general formula (25) are listed below as A-1 to A-27, but the monomers that can be employed in the present invention are limited to these specific examples. It is not a thing.

[Other monomers]
In the present invention, other types of monomers copolymerizable with the monomer having the unit structure represented by the general formulas (12), (21) to (23) and (25) include Polymer Handbook 2nd ed. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1-483 can be used.

  Specifically, for example, 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, dialkyl esters of the above fumaric acid, monoalkyl esters, and the like.

  Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, 2-phenylstyrene and the like.

  Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, and benzyl acrylate. , Benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, methoxy Examples include benzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.

  Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl group having 1 carbon atom). ~ 6), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide (as alkyl groups). Are those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the allyl compound include allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Etc.

  Examples of the vinyl ethers include alkyl vinyl ethers (alkyl groups 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, 1-methyl Examples include -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.

  Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl lactate Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, and the like.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl esters or monoalkyl esters of the fumaric acid include dibutyl fumarate.

  In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile, and the like can also be mentioned.

  Specific examples include the following, but the monomers that can be employed in the present invention are not limited to these specific examples. In the following, n represents an integer of 1 or more.

  The weight average molecular weight of the thermoplastic resin (1) used in the present invention is preferably 1,000 to 500,000, more preferably 3,000 to 300,000, and 10,000 to 100,000. It is particularly preferred that When the weight average molecular weight of the thermoplastic resin (1) is 500,000 or less, the moldability tends to be improved, and when it is 1,000 or more, the mechanical strength tends to be improved.

  Here, the above-mentioned weight average molecular weight was determined by using a GPC analyzer using a column of “TSKgel GMHxL”, “TSKgel G4000HxL”, and “TSKgel G2000HxL” (both trade names manufactured by Tosoh Corporation) with a solvent tetrahydro. The molecular weight is expressed in terms of polystyrene by furan and differential refractometer detection.

  In the thermoplastic resin (1) used in the present invention, the average number of functional groups bonded to inorganic fine particles is preferably from 0.1 to 20, and preferably from 0.5 to 10, per polymer chain. More preferably, it is particularly preferably 1 to 5. If the content of the functional group is 20 or less on average per polymer chain, the thermoplastic resin (1) is coordinated with a plurality of inorganic fine particles to prevent high viscosity and gelation in solution. It tends to be easy. Moreover, if the number of average functional groups per polymer chain is 0.1 or more, the inorganic fine particles tend to be dispersed stably.

  The glass transition temperature of the thermoplastic resin (1) used in the present invention is preferably 85 ° C to 400 ° C, and more preferably 130 ° C to 380 ° C. If a resin having a glass transition temperature of 80 ° C. or higher is used, an optical component having sufficient heat resistance can be easily obtained, and if a resin having a glass transition temperature of 400 ° C. or lower is used, molding tends to be easily performed.

  When the difference between the refractive index of the thermoplastic resin (1) and the refractive index of the inorganic fine particles is large, Rayleigh scattering is likely to occur, so that the amount of fine particles that can be combined while maintaining transparency is reduced. If the thermoplastic resin (1) has a refractive index of about 1.48, a transparent molded article having a refractive index of 1.60 can be provided. The refractive index of the thermoplastic resin (1) used in the invention is preferably 1.55 or more, and more preferably 1.58 or more. These refractive indexes are values at 22 ° C. and a wavelength of 589 nm.

  The thermoplastic resin (1) used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 70% or more, more preferably 80% or more, and 85% or more. More preferably, it is particularly preferably 88% or more.

  Although the preferable specific example of the thermoplastic resin which can be used by this invention is given to the following, the thermoplastic resin which can be used by this invention is not limited to these.

  These thermoplastic resins (1) may be used alone or in combination of two or more. Moreover, you may use together with a thermoplastic resin (2) and / or (3).

Thermoplastic resin (2)
The thermoplastic resin (2) used in the present invention has a functional group capable of forming a chemical bond with inorganic fine particles at at least one position of the polymer terminal. Here, the functional group may be present only at one end of the polymer chain or may be present at both ends, but is preferably present only at one end of the polymer chain. Further, a plurality of functional groups may exist at the terminal. The term “terminal” as used herein means a portion excluding a structure sandwiched between repeating units constituting a polymer chain. Here, the “chemical bond” can be considered in the same manner as the thermoplastic resin (1).

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基である。 Functional groups that can form chemical bonds with inorganic fine particles

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. ] One or more functional groups selected from the group consisting of

The preferred ranges of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are the following ranges.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group. Substituted alkyl groups include, for example, aralkyl groups. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group. The aryl group preferably has 6 to 30 carbon atoms, more preferably 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 herein includes a heteroaryl group. As substituents for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, in addition to these alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) And alkoxy groups (for example, methoxy group, ethoxy group). R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
Preferable ranges of R ¹⁷ and R ¹⁸ are the same as those of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ . n is preferably 3.

−ＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1であり、より好ましくは、

−ＳＯ₃Ｈまたはその塩、あるいは、−ＣＯ₂Ｈまたはその塩であり、さらに好ましくは、

あるいは、−ＣＯ₂Ｈまたはその塩である。 Among these functional groups, preferably

-SO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -Si a ^{_{(OR 15) m1 R 16 3}} -m1, more preferably,

—SO ₃ H or a salt thereof, or —CO ₂ H or a salt thereof, more preferably

Alternatively, it is —CO ₂ H or a salt thereof.

  The basic skeleton of the thermoplastic resin (2) used in the present invention is not particularly limited, and poly (meth) acrylic acid ester, polystyrene, polyvinylcarbazole, polyarylate, polycarbonate, polyurethane, polyimide, polyether, polyethersulfone, Known resin skeletons such as polyether ketone, polythioether, cycloolefin polymer, and cycloolefin copolymer can be employed. Preferred are vinyl polymers, polyarylate, and aromatic-containing polycarbonates, and more preferred are vinyl polymers. Specific examples thereof are the same as those described in the thermoplastic resin (1).

  The thermoplastic resin (2) used in the present invention preferably has a refractive index greater than 1.50, more preferably greater than 1.55, even more preferably greater than 1.60, and greater than 1.65. It is particularly preferred. The refractive index in the present invention is a value measured with respect to light having a wavelength of 589 nm using an Abbe refractometer (manufactured by Atago Co., Ltd., “DR-M4”).

  The thermoplastic resin (2) used in the present invention preferably has a glass transition temperature of 50 ° C to 400 ° C, more preferably 85 ° C to 380 ° C. By setting the glass transition temperature to 50 ° C. or higher, heat resistance tends to be improved, and by setting the glass transition temperature to 400 ° C. or lower, molding processing tends to be easily performed.

  The thermoplastic resin (2) used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 70% or more, more preferably 80% or more, and 85% or more. It is particularly preferred.

  The number average molecular weight of the thermoplastic resin (2) used in the present invention is 1,000 to 500,000. The number average molecular weight of the thermoplastic resin (2) is preferably 3,000 to 300,000, more preferably 5,000 to 200,000, and particularly preferably 10,000 to 100,000. preferable. When the number average molecular weight of the thermoplastic resin (2) is 1,000 or more, the mechanical strength tends to be improved, and when the number average molecular weight is 500,000 or less, the moldability tends to be improved. is there.

  The method for introducing the functional group at the end of the polymer chain is not particularly limited. For example, New Polymer Experiments 4 Polymer Synthesis and Reaction (3) Polymer Reaction and Degradation (Edited by Polymer Society) As described in Chapter 3 “Terminal Reactive Polymer”, it may be introduced at the time of polymerization, or after polymerization, terminal functional group conversion or main chain decomposition of the once isolated polymer may be performed. A method for obtaining a polymer by polymerization using an initiator, a terminator, a chain transfer agent, etc. having a functional group and / or a protected functional group, for example, a phenol terminal portion of a polycarbonate obtained from bisphenol A, It is also possible to use a polymer reaction such as a method of modifying with a contained reactive agent. For example, the serial transfer method vinyl using the sulfur-containing chain transfer agent described in the paragraphs 110 to 112 in “New Polymer Experimental 2 Synthesis and Reaction of Polymers (1) Synthesis of Addition Polymers (Edited by Polymer Society)” Polymeric radical polymerization; functional group-containing initiators according to 255-256, “New Polymer Experiment 2, Synthesis and Reaction of Polymers (1) Synthesis of Addition Polymers” Or, living cationic polymerization using a functional group-containing terminator; ring-opening metathesis polymerization using a sulfur-containing chain transfer agent described in “Macromolecules, Vol. 36”, paragraphs 7020 to 7026 (2003).

  These thermoplastic resins (2) may be used alone or in combination of two or more. Further, these thermoplastic resins may contain other copolymer components.

Thermoplastic resin (3)
The thermoplastic resin (3) used in the present invention is a block copolymer composed of a hydrophobic segment and a hydrophilic segment.

Here, the hydrophobic segment (A) refers to a segment having a characteristic that a polymer composed only of the segment (A) does not dissolve in water or methanol, and the hydrophilic segment (B) includes only the segment (B). A segment in which the polymer has the property of being dissolved in water or methanol. The block copolymer types include AB type, B ¹ AB ² type (two hydrophilic segments B ¹ and B ² may be the same or different) and A ¹ BA ² type (two hydrophobic types). Segments A ¹ and A ² may be the same or different), and from the viewpoint of good dispersion characteristics, AB type or A ¹ BA ² type block copolymers are preferred, and from the viewpoint of production suitability, AB type or ABA type (the two hydrophobic segments of A ¹ BA ² type are the same type) is more preferred, and AB type is particularly preferred.

  The hydrophobic segment and the hydrophilic segment are each a vinyl polymer, polyether, ring-opening metathesis polymer, and condensation polymer (polycarbonate, polyester, polyamide, polyetherketone, polyethersulfone, etc.) obtained by polymerization of vinyl monomers. However, vinyl polymers, ring-opening metathesis polymerization polymers, polycarbonates, and polyesters are preferable, and vinyl polymers are more preferable from the viewpoint of production suitability.

As a vinyl monomer (A) which forms the said hydrophobic segment (A), the following are mentioned, for example.
Acrylic acid esters and methacrylic acid esters (the ester group is a substituted or unsubstituted aliphatic ester group, a substituted or unsubstituted aromatic ester group, such as a methyl group, a phenyl group, or a naphthyl group);

  Acrylamides, methacrylamides, specifically, N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides, N-disubstituted methacrylamides (substituents of mono- and di-substituted products are A substituted or unsubstituted aliphatic group, a substituted or unsubstituted aromatic group, and examples of the substituent include a methyl group, a phenyl group, and a naphthyl group);

  Olefins, specifically, dicyclopentadiene, norbornene derivatives, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, vinylcarbazole and the like; Styrenes, specifically styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, tribromo styrene, vinyl benzoate Acid methyl ester, etc .;

  Vinyl ethers, specifically methyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, methoxyethyl vinyl ether, etc .; other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate , Dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylene malononitrile, vinylidene, diphenyl 2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Chiruhosufeto, dioctyl-2-methacryloyloxyethyl phosphate.

  Among them, acrylic esters and methacrylic esters in which the ester group is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group; the substituent is an unsubstituted aliphatic group, substituted or unsubstituted aromatic group N-monosubstituted acrylamides, N-disubstituted acrylamides, N-monosubstituted methacrylamides and N-disubstituted methacrylamides; styrenes; preferred are acrylic esters and methacrylic esters in which the ester group is a substituted or unsubstituted aromatic group Acid esters; styrenes are more preferred.

As a vinyl monomer (B) which forms the said hydrophilic segment (B), the following are mentioned, for example.
Acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester moiety; styrenes having a hydrophilic substituent at the aromatic ring portion; vinyl ethers having a hydrophilic substituent, acrylamide , Methacrylamide, N-monosubstituted acrylamide, N-disubstituted acrylamide, N-monosubstituted methacrylamide and N-disubstituted methacrylamide.

［Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶は、それぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表す。］、−ＳＯ₃Ｈまたはその塩、−ＯＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−ＯＨ、および、−Ｓｉ（ＯＲ¹⁷）_nＲ¹⁸ _n［Ｒ¹⁷、Ｒ¹⁸はそれぞれ独立に水素原子、置換または無置換のアルキル基、置換または無置換のアルケニル基、置換または無置換のアルキニル基、置換または無置換のアリール基、あるいは、塩を形成しうる原子または基を表し、ｎは１〜３の整数を表す。］からなる群より選択される１以上の官能基である。 As the hydrophilic substituent,

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. ] One or more functional groups selected from the group consisting of

The preferred ranges of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are the following ranges.
The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group. Substituted alkyl groups include, for example, aralkyl groups. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and examples thereof include a benzyl group and a p-methoxybenzyl group. The alkenyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and examples thereof include a vinyl group and a 2-phenylethenyl group. The alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and examples thereof include an ethynyl group and a 2-phenylethynyl group. The aryl group preferably has 6 to 30 carbon atoms, more preferably 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 herein includes a heteroaryl group. As substituents for alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, in addition to these alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, halogen atoms (eg, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms) And alkoxy groups (for example, methoxy group, ethoxy group). R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
Preferable ranges of R ¹⁷ and R ¹⁸ are the same as those of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ . n is preferably 3.

−ＳＯ₃Ｈまたはその塩、−ＣＯ₂Ｈまたはその塩、−Ｓｉ（ＯＲ¹⁵）_m1Ｒ¹⁶ _3-m1であり、より好ましくは、

あるいは、−ＣＯ₂Ｈまたはその塩であり、さらに好ましくは、

である。 Among these functional groups, preferably

-SO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -Si a ^{_{(OR 15) m1 R 16 3}} -m1, more preferably,

Alternatively, a -CO ₂ H or a salt thereof, more preferably,

It is.

  In the present invention, it is particularly preferable to use a thermoplastic resin in which the block copolymer contains the functional group at 0.05 mmol / g to 5.0 mmol / g.

  Among them, as the hydrophilic segment (B), acrylic acid, methacrylic acid, acrylic acid esters and methacrylic acid esters having a hydrophilic substituent at the ester site, and styrenes having a hydrophilic substituent at the aromatic ring portion Is preferred.

  The vinyl monomer (A) forming the hydrophobic segment (A) may contain the vinyl monomer (B) as long as the hydrophobic properties are not hindered. The molar ratio of the vinyl monomer (A) and the vinyl monomer (B) contained in the hydrophobic segment (A) is preferably 100: 0 to 60:40.

  The vinyl monomer (B) forming the hydrophilic segment (B) may contain the vinyl monomer (A) as long as the hydrophilic property is not hindered. The molar ratio of the vinyl monomer (B) and the vinyl monomer (A) contained in the hydrophilic segment (B) is preferably 100: 0 to 60:40.

  Each of the vinyl monomer (A) and the vinyl monomer (B) may be used alone or in combination of two or more. The vinyl monomer (A) and the vinyl monomer (B) are used for various purposes (for example, adjustment of acid content, adjustment of glass transition point (Tg), adjustment of solubility in organic solvents and water, and adjustment of dispersion stability. ).

The content of the functional group is preferably 0.05 to 5.0 mmol / g, more preferably 0.1 to 4.5 mmol / g, based on the entire block copolymer. It is particularly preferably 15 to 3.5 mmol / g. If the content of the functional group is too small, the dispersibility may be reduced. If the content is too large, the water solubility may be too high, or the organic-inorganic composite composition may be gelled. In the block copolymer, the functional group may form a salt with a cationic ion such as an alkali metal ion (for example, Na ⁺ or K ⁺ ) or an ammonium ion.

  The molecular weight (Mn) of the block copolymer is preferably 1000 to 100,000, more preferably 2000 to 80000, and particularly preferably 3000 to 50000. When the molecular weight of the block copolymer is 1000 or more, a stable dispersion tends to be easily obtained, and when it is 100000 or less, the solubility in an organic solvent tends to be improved.

  The block copolymer used in the present invention preferably has a refractive index of more than 1.50, more preferably 1.55 or more, further preferably more than 1.60, and more than 1.65. Is particularly preferred. Here, the refractive index is a value measured with respect to light having a wavelength of 589 nm using an Abbe refractometer (Atago "DR-M4").

  The block copolymer used in the present invention preferably has a glass transition temperature of 85 ° C to 400 ° C, more preferably 130 ° C to 380 ° C. When the glass transition temperature is 80 ° C. or higher, the heat resistance tends to be improved, and when the glass transition temperature is 400 ° C. or lower, the moldability tends to be improved.

  The block copolymer used in the present invention preferably has a light transmittance in terms of 1 mm thickness at a wavelength of 589 nm of 70% or more, more preferably 80% or more, and particularly preferably 85% or more. preferable.

  The block copolymer can be synthesized using living radical polymerization and living ion polymerization using a technique for protecting a carboxyl group or the like as required or introducing a functional group into the polymer. Moreover, it can synthesize | combine by the radical polymerization from a terminal functional group polymer, and the connection of terminal functional group polymers. Among them, it is preferable to use living radical polymerization and living ion polymerization from the viewpoint of molecular weight control and the yield of the block copolymer. As for the production method of the block copolymer, for example, “Synthesis and Reaction of Polymer (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1992))”, “Precision Polymerization (Edited by Chemical Society of Japan, (Published by Academic Publishing Center (1993)) ”,“ Synthesis and Reaction of Polymers (1) (Edited by Polymer Society, Kyoritsu Publishing Co., Ltd. (1995)) ”,“ Telechelic Polymers: Synthesis, Properties, Applications (R) Jerome et al., Prog. Polym. Sci. Vol 16.837-906 (1991)), “Synthesis of block and graft copolymers by light (Y. Yagch et al., Prog. Polym. Sci. Vol 15.551-601). Page (1990)), US Pat. No. 5,085,698 and the like.

  These resins may be used alone or in combination of two or more.

[Plasticizer]
If the glass transition temperature of the resin is high, molding may not always be easy. For this reason, a plasticizer may be used in the present invention in order to lower the molding temperature. As a plasticizer used by this invention, what has a structure represented by General formula (32) is preferable.

（式中、Ｂ¹ およびＢ² は炭素数６〜１８のアルキル基またはアリールアルキル基、ｍは０または１、Ｘは

(Wherein B ¹ and B ² are alkyl or arylalkyl groups having 6 to 18 carbon atoms, m is 0 or 1, and X is

のうちのいずれかであり、Ｒ¹ およびＲ² は水素原子または炭素数４以下のアルキル基を示す。）

R ¹ and R ^{2 each} represent a hydrogen atom or an alkyl group having 4 or less carbon atoms. )

In the compound represented by the general formula (32), B ¹ and B ² may be any alkyl group or arylalkyl group within the range of 6 to 18 carbon atoms. If the number of carbon atoms is less than 6, the molecular weight may be too low to boil at the melting temperature of the polymer and generate bubbles. On the other hand, when the number of carbon atoms exceeds 18, the compatibility with the polymer is deteriorated, so that the effect of addition is insufficient.
Specific examples of the groups B ¹ and B ² include n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group and the like. Straight alkyl groups, branched alkyl groups such as 2-hexyldecyl group and methyl-branched octadecyl group, and arylalkyl groups such as benzyl group and 2-phenylethyl group. Specific examples of the compound represented by the general formula (32) used in the present invention include the following compounds, among which W-1 (trade name [KP-L155] manufactured by Kao Corporation) is preferable.

[Inorganic fine particles]
Examples of the inorganic fine particles used in the present invention include oxide fine particles and sulfide fine particles. More specifically, examples include zirconium oxide fine particles, zinc oxide fine particles, titanium oxide fine particles, tin oxide fine particles, and zinc sulfide fine particles, but are not limited thereto. Among these, metal oxide fine particles are particularly preferable, and among them, any one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide, and titanium oxide is preferable, and includes zirconium oxide, zinc oxide, and titanium oxide. More preferably, it is any one selected from the group, and it is particularly preferable to use zirconium oxide fine particles having good visible range transparency and low photocatalytic activity. In the present invention, these inorganic composites may be used from the viewpoints of refractive index, transparency, and stability. These fine particles are doped with different elements for various purposes such as photocatalytic activity reduction and water absorption reduction, the surface layer is coated with different metal oxides such as silica and alumina, silane coupling agents, titanate coupling agents. For example, the surface may be modified.

  The method for producing inorganic fine particles used in the present invention is not particularly limited, and any known method can be used. For example, desired oxide fine particles can be obtained by using a metal halide or an alkoxy metal as a raw material and hydrolyzing in a reaction system containing water.

  Specifically, as a method for obtaining zirconium oxide fine particles or suspensions thereof, an aqueous solution containing a zirconium salt is neutralized with an alkali to obtain hydrated zirconium, dried and fired, dispersed in a solvent, and suspended in zirconium oxide. A method of obtaining a suspension; A method of hydrolyzing an aqueous solution containing a zirconium salt to obtain a zirconium oxide suspension; A method of hydrolyzing an aqueous solution containing a zirconium salt to obtain a zirconium oxide suspension, and then ultrafiltration. A method of hydrolyzing zirconium alkoxide to obtain a zirconium oxide suspension; and a method of obtaining a zirconium oxide suspension by heat-treating an aqueous solution containing a zirconium salt under hydrothermal pressure, and the like are known. Any of these methods may be used.

  Further, titanyl sulfate is exemplified as a raw material for synthesizing titanium oxide fine particles, and zinc salts such as zinc acetate and zinc nitrate are exemplified as synthetic raw materials for zinc oxide nanoparticles. Metal alkoxides such as tetraethoxysilane and titanium tetraisopropoxide are also suitable as raw materials for inorganic fine particles. As a method for synthesizing such inorganic fine particles, for example, Japanese Journal of Applied Physics, Vol. 37, pages 4603-4608 (1998), or Langmuir, Vol. 16, No. 1, pages 241-246 (2000). ).

  In particular, when the oxide nanoparticles are synthesized by the sol generation method, for example, as in the synthesis of titanium oxide nanoparticles using titanyl sulfate as a raw material, this is passed through a precursor such as hydroxide, and then this is oxidized with acid or alkali. Procedures to form hydrosols by dehydration condensation or peptization are also possible. In the procedure via such a precursor, it is preferable from the viewpoint of the purity of the final product that the precursor is isolated and purified by any method such as filtration or centrifugation. An appropriate surfactant such as sodium dodecylbenzenesulfonate (abbreviated as DBS) or dialkylsulfosuccinate monosodium salt (trade name “Eleminol JS-2” manufactured by Sanyo Chemical Industries, Ltd.) is added to the resulting hydrosol. The sol particles may be isolated by making them water-insoluble. For example, a known method described in “Coloring Materials” Vol. 57, No. 6, pp. 305-308 (1984) can be used.

Further, as a method other than the method of hydrolyzing in water, a method of producing inorganic fine particles in an organic solvent can also be mentioned. At this time, the thermoplastic resin used in the present invention may be dissolved in the organic solvent.
Examples of the solvent used in these methods include acetone, 2-butanone, dichloromethane, chloroform, toluene, ethyl acetate, cyclohexanone, anisole and the like. These may be used alone or as a mixture of two or more.

If the number average particle size of the inorganic fine particles used in the present invention is too small, the characteristics specific to the substance constituting the fine particles may change. Conversely, if the number average particle size is too large, the influence of Rayleigh scattering becomes remarkable, and the organic-inorganic composite composition The transparency of the object may be extremely reduced. Therefore, the lower limit of the number average particle size of the inorganic fine particles used in the present invention is preferably 1 nm or more, more preferably 2 nm or more, further preferably 3 nm or more, and the upper limit is preferably 30 nm or less, more preferably 15 nm. Hereinafter, it is more preferably 10 nm or less, particularly preferably 7 nm or less. That is, the number average particle size of the inorganic fine particles in the present invention is preferably 1 nm to 15 nm, more preferably 2 nm to 10 nm, and particularly preferably 3 nm to 7 nm.
Here, the above-mentioned number average particle size can be measured by, for example, an X-ray diffraction (XRD) apparatus or a transmission electron microscope (TEM).

  The range of the refractive index of the inorganic fine particles used in the present invention is preferably 1.9 to 3.0 at a wavelength of 589 nm at 22 ° C., more preferably 2.0 to 2.7, particularly preferably. 2.1 to 2.5. If the refractive index of the fine particles is 3.0 or less, the difference in refractive index from the thermoplastic resin is not so large, and Rayleigh scattering tends to be easily suppressed. Moreover, if the refractive index is 1.9 or more, there is a tendency that a high refractive index is easily achieved.

  The refractive index of the inorganic fine particles is measured separately by, for example, measuring the refractive index with an Abbe refractometer (for example, “DM-M4” manufactured by Atago Co., Ltd.) using a composite compounded with the thermoplastic resin used in the present invention as a transparent film. It can be estimated by a method of converting from the refractive index of only the resin component, or a method of calculating the refractive index of the fine particles by measuring the refractive index of the fine particle dispersion having different concentrations.

  The content of the inorganic fine particles in the organic-inorganic composite composition of the present invention is preferably 20 to 95% by mass, more preferably 25 to 70% by mass, and 30 to 60% by mass from the viewpoint of transparency and high refractive index. Particularly preferred. In addition, the mass ratio of the inorganic fine particles and the thermoplastic resin (dispersed polymer) in the present invention is preferably 1: 0.01 to 1: 100, and preferably 1: 0.05 to 1:10, from the viewpoint of dispersibility. Further preferred is 1: 0.05 to 1: 5.

[Method for producing organic-inorganic composite composition]
The organic-inorganic composite composition of the present invention can be produced by mixing components such as a thermoplastic resin and inorganic fine particles.
Since the inorganic fine particles used in the present invention have a relatively small particle size and high surface energy, it is difficult to re-disperse when isolated as a solid. Therefore, the inorganic fine particles are preferably mixed with the thermoplastic resin in a state of being dispersed in a solution to form a stable dispersion. As a preferable production method of the composite composition, (1) inorganic particles are surface-treated in the presence of the surface treatment agent, the surface-treated inorganic fine particles are extracted in an organic solvent, and the extracted inorganic fine particles are A method of producing a composite composition of inorganic fine particles and a thermoplastic resin by uniformly mixing with a thermoplastic resin, (2) Mixing both uniformly using a solvent capable of uniformly dispersing or dissolving both the inorganic fine particles and the thermoplastic resin. And a method for producing a composite composition of inorganic fine particles and a thermoplastic resin.

When a composite composition of inorganic fine particles and a thermoplastic resin is produced by the method of (1) above, water-insoluble water such as toluene, ethyl acetate, methyl isobutyl ketone, chloroform, dichloroethane, dichloroethane, chlorobenzene, and methoxybenzene is used as the organic solvent. Sex solvents are used. The surface treatment agent used for extraction of the fine particles into the organic solvent and the thermoplastic resin may be the same or different, but the surface treatment agent preferably used is described above Those described in the section of> are mentioned.
When mixing the inorganic fine particles extracted into the organic solvent and the thermoplastic resin, additives such as a plasticizer, a release agent, or another type of polymer may be added as necessary.

  In the case of the above (2), the solvent is hydrophilic such as dimethylacetamide, dimethylformamide, dimethylsulfoxide, benzyl alcohol, cyclohexanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, t-butanol, acetic acid, propionic acid, etc. Preferably, a polar solvent alone or mixed solvent, or a mixed solvent of chloroform, dichloroethane, dichloromethane, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, chlorobenzene, methoxybenzene or the like and a polar solvent mentioned above is preferably used. . At this time, a dispersing agent, a plasticizer, a release agent, or another type of polymer may be added as necessary in addition to the above-described thermoplastic resin. When using fine particles dispersed in water / methanol, add a hydrophilic solvent that has a higher boiling point than water / methanol and dissolve the thermoplastic resin, and then concentrate the water / methanol to disperse the fine particles. After replacing the liquid with a polar organic solvent, it is preferable to mix with the resin. At this time, the surface treatment agent may be added.

  The solution of the organic-inorganic composite composition obtained by the methods (1) and (2) can be cast as it is to obtain a transparent molded body. In the present invention, however, the solution is particularly concentrated and freeze-dried. Alternatively, after removing the solvent by a method such as reprecipitation from an appropriate poor solvent, the solidified powder is preferably molded by a known method such as injection molding or compression molding. At this time, the powdery organic-inorganic composite composition of the present invention can be processed into a molded article such as a lens by directly heating, melting, or compressing, but once it has a certain weight and shape by a method such as an extrusion method. After forming a preform (precursor) having, an optical component such as a lens can be formed by deforming the preform by compression molding. In this case, the preform can have an appropriate curvature in order to efficiently create the target shape.

  The organic-inorganic composite composition may be used as a master batch by mixing with other resins.

［上式において、γ_s ^pは温度２５℃・相対湿度６０％の条件下で測定した前記有機無機複合組成物の表面自由エネルギーの極性成分（ｍＮ／ｍ）であり、Ｅは前記有機無機複合組成物の破断エネルギー密度（Ｊ／ｍ²）である。］ The organic-inorganic composite composition of the present invention satisfies the following formula (1).

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), E is the organic-inorganic composite It is the breaking energy density (J / m ² ) of the composition. ]

The organic-inorganic composite composition of the present invention preferably satisfies the following formula (1a), more preferably satisfies the formula (1b), and satisfies the formula (1c). Is more preferable.

Gamma _s ^p of the organic-inorganic hybrid composition of the present invention is usually less than 3.5 mN / m, is preferably 2.0 mN / m, more preferably at most 1.0 mN / m. γ _s ^p can be adjusted, for example, by controlling the amount of functional groups in the thermoplastic resin and controlling the diameter of the inorganic fine particles.
The breaking energy density E of the organic-inorganic composite composition of the present invention is preferably 30 J / m ² or more, more preferably 50 J / m ² or more, and further preferably 100 J / m ² or more. The breaking energy density can be adjusted by controlling the monomer unit type and monomer unit content of the thermoplastic resin.

[Optical parts]
The optical component of the present invention can be produced by molding the organic-inorganic composite composition of the present invention described above. As the optical component of the present invention, those showing the refractive index and optical characteristics described above in the explanation of the organic-inorganic composite composition are useful.
In addition, as the optical component of the present invention, a high refractive index optical component having a thickness of at most 0.1 mm is particularly useful. It is preferably applied to an optical component having a thickness of 0.1 to 5 mm, and particularly preferably applied to a transparent article having a thickness of 1 to 3 mm.
These thick molded products are difficult to remove by solvent casting and are usually not easy, but by using the organic-inorganic composite composition of the present invention, molding is easy and complex shapes such as aspherical surfaces are easy. Therefore, an optical component having good transparency can be obtained using the high refractive index characteristics of the fine particles.

  The optical component using the organic-inorganic composite composition of the present invention is not particularly limited as long as it is an optical component using the excellent optical properties of the organic-inorganic composite composition of the present invention. It can also be used for optical components that transmit light (so-called passive optical components). Functional devices including such optical components include various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), cameras, videos, etc. The imaging device is exemplified. Examples of the passive optical component in such an optical functional device include a lens, a prism, a prism sheet, a panel, a film, an optical waveguide, an optical disc, an LED sealing agent, and the like.

An optical component using the organic-inorganic composite composition of the present invention is particularly suitable for a lens substrate. The lens substrate manufactured using the organic-inorganic composite composition of the present invention has both light transmittance and light weight, and is excellent in optical properties. In addition, the refractive index of the lens substrate can be arbitrarily adjusted by appropriately adjusting the type of monomer constituting the organic-inorganic composite composition and the amount of inorganic fine particles to be dispersed.
The “lens substrate” in the present invention means a single member capable of exhibiting a lens function. A film or a member can be provided on the surface or the periphery of the lens substrate according to the use environment or application of the lens. For example, a protective film, an antireflection film, a hard coat film, or the like can be formed on the surface of the lens substrate. Further, the periphery of the lens base material can be fitted and fixed to a base material holding frame or the like. However, these films and frames are members added to the lens base material referred to in the present invention, and are distinguished from the lens base material itself referred to in the present invention.

  When the lens substrate in the present invention is used as a lens, the lens substrate itself of the present invention may be used alone as a lens, or may be used as a lens with a film or a frame added as described above. . The type and shape of the lens using the lens substrate of the present invention are not particularly limited. The lens substrate of the present invention is, for example, an eyeglass lens, an optical device lens, an optoelectronic lens, a laser lens, a pickup lens, an imaging lens (an in-vehicle camera lens, a portable camera lens, a digital camera lens, etc .; (Including various known imaging lenses such as zoom lenses and positive / negative power lenses), OHP lenses, microlens arrays, and the like).

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Analysis and Evaluation Method]
(1) Evaluation of mold residue After the heat molding, the mold residue when the molded body was removed from the mold made of stainless steel was subjected to sensory evaluation based on the following criteria.
○: No mold residue △: Mold residue is small ×: Mold residue is large

(2) Light transmittance measurement A resin material or an organic-inorganic composite composition to be measured was molded to prepare a sample having a thickness of 1.0 mm, and measured with an ultraviolet-visible absorption spectrum measuring apparatus UV-3100 (manufactured by Shimadzu Corporation). .

(3) Refractive index measurement Light having a wavelength of 589 nm was measured with an Abbe refractometer (DR-M4 manufactured by Atago Co., Ltd.).

(4) Contact angle Using a contact angle meter (CA-X type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.), using pure water and iodocamethylene as liquids in a dry state (20 ° C./65% RH). Then, a droplet having a diameter of 1.0 mm was formed on the tip of the needle, and this was brought into contact with the surface of the sample to form a droplet on the sample. The angle formed by the sample and the tangent to the liquid surface at the point where the sample and the liquid are in contact with each other is defined as the contact angle.

(5) Surface free energy The surface free energy can be determined by a contact angle method, a wet heat method, and an adsorption method. In the present invention, the contact angle method is preferably used.
Specifically, pure water and iodocamethylene, whose surface free energy is known, are dropped onto the sample, and at the intersection between the surface of the droplet and the sample surface, the liquid makes a tangential line drawn by the droplet and the angle formed by the sample surface. The surface free energy of the sample can be calculated by defining the angle containing the droplet as the contact angle and applying it to the following formulas (2) and (3).

(6) Energy per cross-sectional area required to destroy the molded body A material composition was formed to prepare a sample of 10 □ × 0.2 mm and conditioned at a temperature of 25 ° C. and a relative humidity of 60% for 24 hours. After that, the SS curve until breakage is measured with a Tensilon universal testing machine RTC-1150A (3-point support mode, indentation speed 2 mm / min) manufactured by A & D Co., Ltd. The integrated value from 0 to the breaking indentation length of the SS curve thus obtained was divided by the breaking cross section to obtain a value.

[Synthesis of materials]
(1) Synthesis of titania fine particles While stirring a 0.1 mol / L titanyl sulfate aqueous solution, a 1.5 mol / L sodium carbonate aqueous solution having the same volume was added dropwise at room temperature over 10 minutes. The white ultrafine particle suspension thus obtained was centrifuged at 3500 rpm and purified by repeating the steps of removing the supernatant by decantation and washing with water. The white precipitate thus obtained was heated at 50 ° C. for about 1 hour with stirring and dispersing in 0.3 mol / L of dilute hydrochloric acid to obtain a transparent acidic hydrosol. This acidic hydrosol was ice-cooled, and an aqueous solution of sodium dodecylbenzenesulfonate was added to form a white precipitate, which was then extracted with toluene, dried and concentrated. From the XRD and TEM of the concentrated residue, it was confirmed that anatase-type titania fine particles (number average particle size was about 5 nm) were formed.

(2) Synthesis of zirconia fine particles A zirconium oxychloride solution having a concentration of 50 g / L was neutralized with a 48% aqueous sodium hydroxide solution to obtain a hydrated zirconium suspension. The suspension was filtered and then washed with ion exchanged water to obtain a hydrated zirconium cake. The cake was adjusted to a concentration of 15% by mass in terms of zirconia using ion-exchanged water as a solvent, placed in an autoclave, and hydrothermally treated at 150 ° C. and 150 ° C. for 24 hours to obtain a zirconia fine particle suspension. The generation of zirconia fine particles having a number average particle size of 5 nm was confirmed by TEM.

(3) Preparation of zirconia fine particle toluene dispersion The zirconia fine particle suspension synthesized in (2) above and a toluene solution in which p-propylbenzoic acid manufactured by Tokyo Kasei was dissolved were mixed and stirred at 50 ° C. for 8 hours. The toluene solution was extracted to prepare a zirconia fine particle toluene dispersion.
When other dispersants are used, they can be prepared by the same method.

(4) Resin synthesis Synthesis of P-3:
To a 300 ml three-neck flask equipped with a reflux condenser and a gas introduction cock, 0.5 g of Silaplane FM-0725 (S-6, n = 131) manufactured by Chisso Corporation was added, and after nitrogen substitution twice, methyl maleimide ( A-2) 7.5 g, styrene (B-1) 41.5 g, 2-carboxyethyl acrylate (C-3) 0.5 g, ethyl acetate 21.4 g, and Wako Pure Chemical Industries, Ltd. V as an initiator -601 0.5g was added, and after nitrogen substitution twice, it heated at 80 degreeC under nitrogen stream for 3 hours. After returning to room temperature, 30 ml of ethyl acetate was added, stirred for 10 minutes, poured into 2 L of methanol, and reprecipitated. The precipitate was collected by filtration, washed with a large amount of methanol, and vacuum-dried at 60 ° C. for 3 hours to obtain P-3 (yield 35%, number average molecular weight 47,000).
Other exemplified polymers can be prepared in a similar manner.

(5) Preparation of organic / inorganic composite composition Toluene dispersion (zirconia: p-propylbenzoic acid = 10: 1) of zirconia fine particles synthesized in (3) was used as resin P-3 and S-manufactured by Matsumura Oil Research Co., Ltd. The solution was added dropwise to a toluene solution in which 3103 was dissolved over 5 minutes, stirred for 1 hour, and then the solvent was removed to obtain an organic-inorganic composite composition as a powder.
Other organic-inorganic composite compositions were prepared in the same manner.

[Manufacture of optical components by thermoforming]
Each lens of Examples 1 to 7 and Comparative Example 1 was manufactured by the following procedure. The types of inorganic fine particles used and the amounts used as inorganic components were as shown in Table 2. However, p-propylbenzoic acid is contained in an amount of 8.3% by mass and S-3103 in an amount of 4.2% by mass, and the remainder is occupied by the resin. In Comparative Example 1, Q-1 (the constituent monomers are 60% by mass of B-1, 40% by mass of C-2, and the number average molecular weight is 15000) is used as the resin.
Each manufactured organic-inorganic composite composition was heat-molded at 180 ° C. to prepare a molded article for a lens having a thickness of 1 mm. At this time, the mold remainder after releasing from the mold was evaluated. The molded body was used for light transmittance measurement, refractive index measurement, and contact angle measurement, and the surface free energy was calculated from the result of the contact angle measurement. In addition, a material composition was formed to prepare a sample of 10 □ × 0.2 mm, and measurement with Tensilon and calculation of breaking energy density were performed. These results are listed in Table 2 below. The lens molded body was then molded into the shape of a lens to obtain a lens as an optical component.

  As is apparent from Table 2, resin materials having excellent mold residue, refractive index greater than 1.60 and good transparency were obtained according to the present invention (Examples 1 to 7). In Comparative Example 1, since the polar component γsp of the surface free energy and the breaking energy density E do not satisfy the formula (1), the mold residue is poor.

  The optical component of the present invention includes a material composition that has both high refraction, light transmittance, and light weight, and a reduced mold residue. ADVANTAGE OF THE INVENTION According to this invention, the optical component which adjusted the refractive index arbitrarily can be provided comparatively easily. Therefore, the present invention is useful for providing a wide range of optical components such as a high refractive lens, and has high industrial applicability.

Claims (20)

An organic-inorganic composite composition comprising a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain, and inorganic fine particles, and satisfying the following formula (1): .

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), E is the organic-inorganic composite It is the breaking energy density (J / m ² ) of the composition. ] The organic-inorganic composite composition composite composition according to claim 1, wherein the breaking energy density is 30.0 J / m ² or more.   The organic-inorganic composite composition according to claim 1, wherein the thermoplastic resin has a glass transition temperature of 85 ° C. or higher. The thermoplastic resin is

[R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, A substituted or unsubstituted aryl group, or an atom or group capable of forming a salt. ], - SO ₃ H or salts thereof, -OSO ₃ H or a salt thereof, -CO ₂ H or a salt thereof, -OH, _{^{and, -Si (OR 17) n R}} 18 n [R 17, R 18 are each independently Represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, or an atom or group capable of forming a salt, n Represents an integer of 1 to 3. The organic-inorganic composite composition according to claim 1, which has one or more functional groups selected from the group consisting of:   The organic-inorganic composite composition according to any one of claims 1 to 4, wherein the thermoplastic resin has an average of 0.1 to 20 functional groups per polymer chain. .   The organic-inorganic composite composition according to any one of claims 1 to 5, wherein the thermoplastic resin has at least one unit structure formed by polymerizing styrene or a styrene derivative. The organic / inorganic according to any one of claims 1 to 6, wherein the thermoplastic resin has at least one unit structure represented by any one of the following general formulas (21) to (23). Composite composition.

[In General Formula (21), R ¹ represents an alkyl group, a perfluoroalkyl group or an aryl group, and n represents an integer of 5 or more. ]

[In General Formula (22), m represents an integer of 1 or more. ]

[In General Formula (23), q represents an integer of 4 or more. ] The organic-inorganic composite composition according to any one of Claims 1 to 7, wherein the thermoplastic resin has a unit structure represented by the following general formula (4).

[In General Formula (4), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a methyl group or a phenyl group, R ⁵ represents a hydrogen atom or an alkyl group, and X consists of an alkylene group or an arylene group. Represents a divalent linking group, and n represents an integer of 5 or more. ] The organic-inorganic composite composition according to any one of claims 1 to 8, wherein the thermoplastic resin has at least one unit structure represented by the following general formula (5).

[In General Formula (5), X represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. ]   The organic-inorganic composite composition according to any one of claims 1 to 9, wherein a particle size of the inorganic fine particles is 1 to 30 nm.   The organic-inorganic composite composition according to any one of claims 1 to 10, wherein the inorganic fine particle is contained in an amount of 20% by mass or more.   The organic-inorganic composite composition according to any one of claims 1 to 11, wherein a light transmittance in terms of thickness of 1 mm is 70% or more at a wavelength of 589 nm.   The organic-inorganic composite composition according to any one of claims 1 to 12, wherein a refractive index at a wavelength of 589 nm is 1.60 or more.   The organic-inorganic composite according to any one of claims 1 to 13, wherein the inorganic fine particles are any one selected from the group consisting of zirconium oxide, zinc oxide, tin oxide and titanium oxide. Composition.   The organic-inorganic composite composition according to any one of claims 1 to 14 is melted and filled in a mold, and after the filled organic-inorganic composite composition is solidified, the molded product is taken out from the mold. A method for producing a molded product.   16. The method for producing a molded article according to claim 15, wherein the molten organic-inorganic composite composition is directly filled into a mold. Selecting an organic-inorganic composite composition containing a thermoplastic resin having a functional group capable of forming an arbitrary chemical bond with inorganic fine particles at the polymer terminal or side chain, and inorganic fine particles, and satisfying the following formula (1): A method for selecting an organic-inorganic composite composition that does not remain in a mold when released from the mold.

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), α is the organic-inorganic composite E is the Young's modulus (N / m ² ) of the organic-inorganic composite composition measured at 25 ° C. and 60% relative humidity. ). ] Mold remaining amount of organic-inorganic composite composition when organic-inorganic composite composition is melted and filled in a mold, and after the filled organic-inorganic composite composition is solidified, a molded product is taken out from the mold A method of suppressing
As the organic-inorganic composite composition, an organic / inorganic material containing a thermoplastic resin having inorganic fine particles and a functional group capable of forming an arbitrary chemical bond at the polymer terminal or side chain and inorganic fine particles and satisfying the following formula (1) A method for suppressing a residual amount of a mold of an organic-inorganic composite composition after taking out a molded product from the mold, wherein the composite composition is selected.

[In the above formula, gamma _s ^p is the surface free energy of the polar component of the organic-inorganic hybrid composition as measured under conditions of a temperature 25 ° C. · RH 60% (mN / m), α is the organic-inorganic composite E is the Young's modulus (N / m ² ) of the organic-inorganic composite composition measured at 25 ° C. and 60% relative humidity. ). ]   The optical component comprised including the organic inorganic composite composition as described in any one of Claims 1-14.   The optical component according to claim 19, wherein the optical component is a lens.