JP2003155415A - Resin composition containing superfine particle and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition-molded product having high transparency, excellent light resistance and a low water absorption at the same time. SOLUTION: The resin composition comprises core/shell type semiconductor superfine particles having a number average particle diameter of 1-50 nm, composed of a core of a semiconductor crystal and a shell of an oxide of at least one element selected from aluminum, silicon, zirconium, tin, and antimony provided on the surface of the core, and has a light transmittance per 1 mm optical path length at the sodium D line wavelength of >=70% and a saturated water absorption, measured under the conditions of 60 deg.C and a relative humidity of 90% in accordance with the ASTM D570 provision, of <=0.4 wt.%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition in which semiconductor ultrafine particles are uniformly dispersed and which has excellent transparency and light resistance. INDUSTRIAL APPLICABILITY The resin composition of the present invention has properties of semiconductor ultrafine particles, such as ultraviolet absorbing ability and excellent heat resistance, and thus is used for various optical member applications.

[0002]

2. Description of the Related Art When utilizing the properties of a non-organic substance such as an inorganic salt, a semiconductor and a metal as a property of a material having excellent moldability, a method of dispersing the non-organic substance as fine particles in an organic resin material is generally used. Is used. In particular, the use of a thermoplastic resin composition is industrially preferable because it enables the use of a manufacturing method having excellent productivity such as injection molding.

In the case of using a method for an optical material that requires a high degree of transparency, the fine particles generally have a refractive index difference from that of the resin matrix, so that at least the particle size is used to reduce light scattering. It is necessary to make the wavelength smaller than the wavelength of the light. Furthermore, in order to reduce the attenuation of the transmitted light intensity due to Rayleigh scattering, the particles are made into ultrafine particles, and especially the particle size is 1
It is preferable to prepare and disperse nanoparticles having a size of less than 0 nm with a particle size distribution as narrow as possible, and the synthesis itself of such nanoparticles is currently the most advanced research subject.

Lenses, prisms, fibers, optical couplers,
Optical members such as transparent panels and transparent substrates are required to have light resistance (especially UV resistance) that can withstand long-time light irradiation. This is a general weakness when comparing organic resin materials with inorganic materials such as glass. In order to improve the weakness of the light resistance of such an organic resin material, conventionally, an ultraviolet absorber which is an organic material having a compatibility that does not impair the transparency of the resin material is added, but the ultraviolet absorber is gradually added. In addition, there is a problem that it decomposes in the resin matrix and causes yellowing and turbidity.

For the purpose of solving these problems, a technique has been proposed in which ultrafine semiconductor particles having an ultraviolet absorbing ability such as zinc oxide and titanium oxide, which are considered to be more durable than organic substances, are dispersed in an organic resin material. There is. Japanese Patent Laid-Open No. 5-2
Japanese Patent No. 21640 discloses a technique relating to a resin composition in which trialkoxysilanes are bonded to the surface of titanium oxide ultrafine particles and dispersed in a resin matrix. In JP-A-11-43556, surface modification is applied to semiconductor ultrafine particles, and a functional group possessed by the surface modification is reacted with a resin (polymer reaction in a solution is particularly preferable).
Thus, a method for obtaining a resin composition having excellent transparency in which semiconductor ultrafine particles are dispersed while suppressing generation of coarse particles and suppressing aggregation is reported. JP-A-2000-230
Japanese Patent Laid-Open No. 107 discloses a technique in which a polymerizable organic compound or the like is bonded to the surface of ultrafine oxide particles of silicon oxide, aluminum oxide, zirconium oxide or the like and dispersed in a crosslinked resin matrix. Japanese Patent Application Laid-Open Nos. 2000-95967 and 2000-281934 disclose techniques for improving the dispersibility in a resin matrix by treating the surface of ultrafine oxide particles with a modified methacrylate or the like. Japanese Patent Laid-Open No. 2001-2417 discloses a technique for improving the dispersibility of titanium oxide ultrafine particles in a resin matrix by using modified polysiloxanes. However, the resin composition technology disclosed by any of these publications is a dispersion technology that is effective for applications such as ultraviolet absorbing coatings and cosmetics for ultraviolet cutting, but when the above optical member is a relatively thick molded body. Was not sufficiently transparent.

Another technical problem that arises when semiconductor ultrafine particles such as zinc oxide and titanium oxide are dispersed in an organic resin material and used is to suppress the photocatalytic activity of decomposing organic substances on the semiconductor crystal surface. This photocatalytic activity is an exciton (exciton, that is, a pair of an electron and a hole) generated by absorption of light by a semiconductor crystal, and at a certain probability, an electron or hole transfer reaction (oxidation-reduction reaction) with an organic substance on the crystal surface.
Is caused, and this reaction is understood to be the activity of decomposing the organic matter.

Several methods for suppressing such photocatalytic activity have been proposed. Japanese Patent Application Laid-Open No. 63-225532 discloses that a titanium oxide crystal having a particle size of 1 to 50 nm has a C content.
o, V, Cr, Mn, Cu, Sb, W, Pt, Hg, P
A technique is disclosed in which a photocatalytic activity is suppressed by doping with a transition metal element selected from b and Bi, and a coating material having improved wear resistance, ultraviolet light shielding, light resistance, and transparency is obtained. Japanese Patent Application Laid-Open No. 08-59238 discloses a technique of suppressing photocatalytic activity and imparting dispersibility to an organic matrix by surface-treating zinc oxide fine particles with an aluminum chelate compound or the like. Japanese Patent Application Laid-Open No. 11-286619 discloses a polyolefin resin-based polymer film in which ultrafine oxide particles of titanium oxide, zinc oxide, cerium oxide or the like having a particle size of 2 to 1000 nm have coordinated anionic polymerization catalytic activity. There is disclosed a technique for improving the dispersibility in the organic matrix while reducing the photocatalytic activity of the ultrafine oxide particles by forming the. Japanese Patent Laid-Open No. 2000-264632 discloses that a metal oxide fine particle having a band gap of 3 to 5 eV and a particle diameter of 10 to 100 nm is adsorbed with a surfactant having a polyoxyalkyl ether chain and further polysiloxane. A technique for improving the dispersion stability while suppressing the photocatalytic activity is disclosed by performing the thin layer coating. In Japanese Patent Laid-Open No. 2001-26423, the surface of rutile type titanium dioxide ultrafine particles having a particle size of 30 nm or less (preferably 5 to 30 nm) synthesized from titanium tetrachloride is coated with alkoxysilane or aminoalkoxysilane. By doing so, a technique is disclosed in which the ultrafine particles are provided with high weather resistance that does not deteriorate the organic components. In Japanese Patent Laid-Open No. 2001-58821, photocatalytic activity is suppressed by applying a coating layer made of zinc silicate to zinc oxide fine particles, and particularly when iron or cobalt is solid-dissolved in zinc oxide crystals, this effect is large. It is disclosed that the fine particles can be further treated with an organic silicon compound, a metal soap or the like in order to improve dispersibility. However, although these techniques are effective in suppressing photocatalytic activity, their dispersibility in an organic resin matrix is still insufficient, and a resin composition having sufficient transparency when used as the above optical member is obtained. I couldn't.

Providing an oxide outer shell of silica or the like on the surface of the semiconductor ultrafine particles as described in each of the publications relating to the method for suppressing the photocatalytic activity is described, for example, in S. Chang
J. et al. Am. Chem. Soc. , Volume 116, 673
9-6744 (1994) and S.S. C. Farmer
Polym. Mater. Sci. Eng, 82
Vol. 237-238 (2000), synthesis of silica-coated cadmium sulfide ultrafine particles (particle size of CdS nanocrystals is about 6 nm, silica-coated ultrafine particles have an average particle size of 52 nm), and H.S. Li et al .; Journal
of Nanoparticle Research
H., Vol. 3, 157-160 (2001), and is also known in the synthesis of silica-coated ultrafine zinc oxide particles. Since a resin composition having excellent transparency could not be obtained by the technique taught by these three documents,
As an improved technique, S. C. Farmer et al .;
Polym. Prepr. (Am. Chem. So
c. , Div. Polym. Chem. ), 42 volumes, 5
78-579 (2001) suppresses photocatalytic activity by generating an acrylic resin such as polymethylmethacrylate by living radical polymerization from a polymerization initiation point fixed on the surface of the above-mentioned silica-coated cadmium sulfide ultrafine particles. It has been reported a resin composition which gives a coating film excellent in strength from a tetrahydrofuran solution. But,
The resin matrix is limited to acrylic resin, and its saturated water absorption is relatively high, which is a problem.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to contain semiconductor ultrafine particles uniformly dispersed therein, and to provide excellent transparency and light resistance (particularly, light resistance). It is intended to provide a resin composition having both (UV resistance) and low water absorption, a molded article made of the resin composition, its use and a manufacturing method.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have determined that semiconductor ultrafine particles having an outer shell (shell) which is an oxide of a specific element have a specific particle size. Was prepared to improve the dispersibility in the resin matrix by binding to its surface an organic ligand that imparts compatibility or reactivity to the transparent resin matrix. Of a resin composition having high water-absorbing property and low water-absorption property can be obtained by a thermoplastic molding method in which the resin composition is heat-pressed under specific temperature conditions or a cross-linking resin molding method using a specific polymerizable monomer. It was found that a molded product having an extremely reduced optical distortion can be obtained in accordance with the above three characteristics, and the present invention has been accomplished.

That is, the first gist of the present invention is an oxide of at least one element selected from aluminum, silicon, zirconium, tin and antimony provided on the inner core (core) which is a semiconductor crystal and the surface thereof. A core-shell type semiconductor ultrafine particle having a number average particle diameter of 1 to 50 nm composed of a certain outer shell is included, and the light transmittance per 1 mm of the optical path length at the sodium D-line wavelength is 70% or more, and A
The resin composition has a saturated water absorption rate of 0.4% by weight or less measured under the conditions of STM D570 standard at 60 ° C. and relative humidity of 90%.

The second gist of the present invention resides in a molded product of the above resin composition, wherein the average of birefringence per 1 mm of the optical path is 10 nm or less. The third gist of the present invention resides in an optical member comprising the above resin composition molded body. A fourth gist of the present invention is that a raw material lump, which is a thermoplastic resin composition in which ultrafine particles are dispersed, is made to have a temperature of 10 to 80 higher than the glass transition temperature of the thermoplastic resin composition.
The method for producing a resin composition molded body, which comprises pressure-molding while keeping the temperature high at a temperature of ℃.

The fifth gist of the present invention resides in the above-mentioned method for producing a resin composition molded body, characterized in that the polymerizable liquid mixture is cured by heat or active energy rays.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Resin Composition] The resin composition of the present invention comprises a transparent resin matrix described below, which includes an inner core which is a semiconductor crystal (hereinafter referred to as “semiconductor core”) and aluminum, silicon, zirconium, tin, which is provided on the surface thereof. Number average particle size 1 to 5 consisting of an outer shell (hereinafter referred to as "oxide shell") which is an oxide of at least one element selected from antimony
It contains 0 nm core-shell type semiconductor ultrafine particles, has a light transmittance of 70% or more per 1 mm of optical path length at a sodium D-line wavelength, and is 6 according to ASTM D570 standard.
The saturated water absorption measured at 0 ° C. and 90% relative humidity is 0.4% by weight or less.

Although the semiconductor crystal will be described later, it serves to impart light resistance (particularly ultraviolet resistance), which is one of the objects of the present invention. That is, due to the property of absorbing light (in particular, ultraviolet rays having a wavelength of 220 to 400 nm) according to the band gap of the semiconductor crystal, it serves to suppress or prevent photodegradation of the resin matrix. The oxide shell mainly serves to block the photocatalytic activity of the semiconductor core. It is considered that this is due to the mechanism in which the exciton generated by the semiconductor core absorbing electromagnetic waves such as ultraviolet rays acts as a barrier that blocks the action of decomposing the resin matrix by the redox reaction. Another role of the oxide shell is to keep the semiconductor core stable by shielding it from chemical reactions from the outside world. For example, water, acid (hydrochloric acid, sulfuric acid,
It is presumed that the function of protecting the performance of the semiconductor core is protected by blocking active chemical species such as acetic acid and the like), bases (caustic alkali and the like), hydrogen sulfide and the like that may have reactivity with semiconductor crystals.

Such an oxide shell is formed by a known metal oxide synthesis method, for example, a metal alkoxide called a vapor deposition method, a so-called sol-gel method, a nitrate salt, an acetate salt, a sulfate salt,
It is formed by a hydrolysis-condensation reaction of a metal salt such as a halide such as chloride, a hot soap method described later, or the like. Preferred oxide shell forming methods in the present invention are a sol-gel method and a hot soap method in terms of suppressing secondary aggregation of the generated core-shell type semiconductor ultrafine particles, and among them, tetraethoxysilane and tetramethoxysilane and these The sol-gel method that can utilize oligomers is the most suitable.
What is preferably used as the chemical composition of the oxide shell in the present invention in terms of chemical stability and easiness of synthesis,
Of these, silicon oxide, aluminum oxide and zirconium oxide are preferred, with silicon oxide and aluminum oxide being more preferred, and silicon oxide being most preferred.

The term "core-shell type" in the present invention means a structure in which the above oxide composition includes an arbitrary number of semiconductor crystals. That is, it may be either a state in which the shell includes one semiconductor crystal or a state in which the shell includes a plurality of semiconductor crystals. In the core-shell type semiconductor ultrafine particles of the present invention, it is desirable that a part of the semiconductor core is not exposed on the surface of the core-shell type semiconductor ultrafine particles. This is because the exposure of the semiconductor core having a high photocatalytic activity may increase the photocatalytic activity of the entire core-shell type semiconductor ultrafine particles. Although the number of semiconductor cores contained in one core-shell type semiconductor ultrafine particle is not limited, it is usually 1 to 2000, but the semiconductor core has properties as a semiconductor crystal (formation of band structure of electron level, etc.). Since it is preferable that the particle diameter of the semiconductor core is 1 nm or more from the viewpoint that it remarkably has, the number of semiconductor cores contained in one core-shell type semiconductor ultrafine particle is preferably 1 to 1.
The number is 000, more preferably 1 to 500, and further preferably 1 to 100.

The content of the semiconductor core in one core-shell type semiconductor ultrafine particle (hereinafter abbreviated as "core content in particles") is one of the objects of the present invention due to the exposure of the semiconductor core. It is preferable that the effect of suppressing the photocatalytic activity is as large as possible unless the effect is remarkably reduced, in order to make the characteristics peculiar to the semiconductor core such as the ultraviolet absorbing ability remarkable. Generally, elemental analysis of core-shell type semiconductor ultrafine particles contained in a given resin composition is performed by thermogravimetric analysis, organic elemental analysis, fluorescent X-ray analysis, solid-state emission analysis, inorganic elemental analysis by dissolving in acid or alkali. It is possible by combining various composition analysis methods such as. Therefore, in the present invention, the core content in the particles in the given core-shell type semiconductor ultrafine particles is at least selected from aluminum, silicon, zirconium, tin and antimony contained in the transition metal element and the oxide shell contained in the semiconductor core. It is evaluated by the molar ratio with one kind of element (hereinafter referred to as “core: shell element ratio”). The value of the core: shell element ratio is usually 0.001 to 10, and the lower limit thereof is preferably 0.0 from the viewpoint of making the characteristics peculiar to the semiconductor core noticeable.
1, more preferably 0.1, while its upper limit is preferably 8 and more preferably 6 from the viewpoint of the effect of suppressing photocatalytic activity.

In the present invention, the particle size of the semiconductor core contained in the core-shell type semiconductor ultrafine particles is usually 0.5 to 40.
nm, and the lower limit thereof is preferably 1 nm, more preferably 2 nm in order to make the characteristics peculiar to the semiconductor core noticeable, while the upper limit thereof is preferably 30 nm in view of the effect of suppressing photocatalytic activity, further preferably It is 20 nm. If the number average particle size of the semiconductor ultrafine particles is too small, the characteristics peculiar to the semiconductor core (for example, the formation of a band structure due to the crystallinity of the semiconductor) may not be remarkable, and conversely the number average particle size is too large. In some cases, the cohesiveness of the semiconductor ultrafine particles may be extremely increased, the transparency and mechanical strength of the resin composition may be extremely decreased, or the characteristics due to the quantum effect (for example, exciton absorption / emission ability in semiconductor crystals) may not be remarkable. . Therefore, the lower limit value of the number average particle diameter is preferably 1 nm, more preferably 2 nm, further preferably 3 nm, and the upper limit value is preferably 40 nm, more preferably 30 nm, still more preferably 20 nm. From the viewpoint of transparency of the resin composition of the present invention, the ratio of ultrafine particles having a particle size of 60 nm or more is usually 10% by volume or less, preferably 5% by volume or less, more preferably 5% by volume or less, based on the volume of all ultrafine particles. Is 3% by volume or less.

Various particle size measurements and the above volume% in the present invention
The numerical value measured from the transmission electron microscope (TEM) observation image is used for the determination. That is, the diameter of a circle having the same area as the observed ultrafine particle image is defined as the particle size of the particle image. The number average particle diameter is calculated, for example, by a known statistical processing method of image data using the particle diameter thus determined, and the number of ultrafine particle images used for the statistical processing (the number of statistically processed data)
Is naturally desirable as much as possible, and in the present invention,
The number of the particle images randomly selected from the viewpoint of reproducibility is at least 50 or more, preferably 80 or more, and more preferably 100 or more. The calculation of the volume% is performed by converting the volume of a sphere having the diameter determined by the above as a diameter.

If the light transmittance (hereinafter referred to as "D-ray transmittance") per 1 mm of the optical path length at the sodium D-ray wavelength that defines the transparency of the resin composition of the present invention is too small, the transparency becomes insufficient. Since the use as an optical member may be hindered, the value of the D-ray transmittance is preferably 8
It is 0% or more, more preferably 85% or more, and most preferably 89% or more.

The resin composition of the present invention is ASTM D57.
It is characterized by a saturated water absorption of 0.4% by weight or less measured at 60 ° C. and a relative humidity of 90% according to 0 standard. This is to sufficiently reduce the dimensional change due to moisture absorption when used as an optical member as described later. The saturated water absorption is preferably 0.3% by weight or less, more preferably 0.2% by weight or less. Such a low water absorption rate cannot be sufficiently achieved by simply using a resin matrix having a low water absorption rate, and is an unexpected feature that becomes remarkable due to the dispersion of the semiconductor ultrafine particles. Although the reason for this is not clear, not only is the effect of mixing semiconductor crystals having substantially no water absorption (the effect expected to be effective at the volume fraction) being observed, but the polymer chains constituting the resin matrix are It is presumed that it is also related to the fact that it is adsorbed to a very large surface area and the mobility of molecular chains is restricted to some extent.

The shape of the semiconductor ultrafine particles used in the resin composition of the present invention has an aspect ratio (long axis) for the purpose of reducing the directional anisotropy of the linear expansion coefficient as the whole of the resin composition molded body described later. And the minor axis) is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Most preferred are spheres (ie aspect ratio 1). The semiconductor ultrafine particles may be used in combination of a plurality of types, and the particle size distribution is not limited, and the semiconductor ultrafine particles having different particle size distributions such as a two-peak distribution may be used in combination.

The resin composition of the present invention was treated under a nitrogen atmosphere at 600
The residue obtained by thermal decomposition at 120 ° C. for 120 minutes is usually 1 to 60% by weight before the thermal decomposition. The amount of such a residue is also an index that reflects the content of the inorganic component (the sum of the semiconductor core and the oxide shell) in the given resin composition. If the amount of the above residue is too small, the characteristics of the semiconductor core may be difficult to develop, so the lower limit value is preferably 3%, more preferably 5%. On the other hand, if the amount of the above residue is too large, the transparency and mechanical strength of the resin composition of the present invention may be extremely deteriorated. Therefore, the upper limit is preferably 50%, more preferably 40%. The measurement of the amount of such residue is
For example, the given resin composition may be heated in an electric furnace in a nitrogen atmosphere, or more simply, thermogravimetric analysis (TG) in a nitrogen atmosphere.

The light absorption property of the resin composition of the present invention is not particularly limited depending on the application to which it is applied, but in applications requiring ultraviolet resistance and ultraviolet shielding properties, a wavelength of 350 n is used.
light transmittance per 1 mm of optical path length in m (hereinafter referred to as “3
It is preferable that the “50 nm transmittance” is 50% or less. The reason for designating the specific wavelength of 350 nm mentioned here is that it is possible to effectively absorb the ultraviolet light having a wavelength of 350 nm or less at which the photodecomposition of the organic resin material becomes remarkable due to the basic absorption of the semiconductor crystal. It is appropriate as an absorption capacity evaluation index. 350 above
When the nm transmittance is too large, the ultraviolet resistance and the ultraviolet shielding property of the resin composition of the present invention may be extremely lowered,
The upper limit is more preferably 30%, further preferably 1
It is 5%, most preferably 5%.

Regarding the heat resistance of the resin composition of the present invention,
The glass transition temperature (Tg) is preferably 150 ° C. or higher. If the glass transition temperature is too low, the heat resistance may be insufficient, so the glass transition temperature is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. The glass transition temperature is measured by a differential thermal analysis (DSC) of a given resin composition, a dynamic viscoelasticity test (so-called tan δ measurement) of a strip of the given resin composition, or a thermomechanical analysis method. (TMA) is carried out by a known method such as softening temperature measurement for measuring mechanical displacement due to heating under a load. The highest measured value is adopted.

The thickness of the oxide shell in the core-shell type semiconductor ultrafine particles is not limited as long as the effect of suppressing the photocatalytic activity is not extremely reduced, but is usually 0.5 to
It is 20 nm. The lower limit is preferably 1 nm, more preferably 2 nm, further preferably 3 nm from the viewpoint of the effect of suppressing photocatalytic activity, while the upper limit is preferably 15 n in order to increase the semiconductor core content and ensure light absorption.
m, more preferably 12 nm, further preferably 10 nm
Is.

In the resin composition of the present invention, it is preferable that the semiconductor ultrafine particles have an organic ligand bonded thereto from the viewpoint of dispersibility. The organic ligand referred to here is an organic molecule bonded to the surface of the ultrafine particles, and will be described in detail later. When such an organic ligand contains a functional group of any one of an amino group, a hydroxyl group, a mercapto group, a carboxyl group, an acryloyl group, a methacryloyl group, and an epoxy group in the molecular structure, the reactivity with the resin matrix It is preferable that the polymer that constitutes the resin matrix in terms of reactivity with these functional groups has any of an ester bond, an amide bond, a carbonate bond, a urethane bond, a urea bond, and a carbon-carbon double bond. That functional group is contained in the polymer structure. The resin forming the resin matrix will be described later. The resin composition of the present invention,
Various additives may be used in combination unless the object of the present invention is significantly deviated. Examples of such additives include stabilizers such as antioxidants, heat stabilizers, or light absorbers, glass fibers, aerosil, silica colloid particles, glass beads, mica, talc, kaolin, clay minerals, metal fibers, metals. Powders, fillers such as metal colloid particles, carbon materials such as carbon fiber, carbon black and graphite, dielectrics such as barium titanate (nano particles are also possible), antistatic agents, plasticizers, release agents, erasers Examples include foaming agents, leveling agents, anti-settling agents, surfactants, modifiers such as thixotropy imparting agents, pigments, dyes, colorants such as hue adjusters, and the like. These additives may be mixed at the time of producing the resin composition, or may be added at the time of molding the resin composition molded body of the present invention described later. The addition amount of these various additives is appropriately set according to the application, but is usually 10
It is not more than 5% by weight, preferably not more than 5% by weight.

[Production Method of Resin Composition] The production method of the resin composition of the present invention is not limited, but, for example, a method of melting or solution mixing the core-shell type semiconductor ultrafine particles and a thermoplastic resin, the core-shell type A method of melting or solution-mixing a masterbatch (high-concentration composition) obtained by melting or solution-mixing semiconductor ultrafine particles and a thermoplastic resin, polymerization of the core-shell type semiconductor ultrafine particles and resin matrix raw material Examples of the method include a method of mixing with a polymerizable monomer and a subsequent polymerization reaction, a method of mixing the masterbatch and a polymerizable monomer as a resin matrix raw material and a subsequent polymerization reaction.

As a preferred procedure, there is a method of previously binding an appropriate organic ligand to the surface of the core-shell type semiconductor ultrafine particles. This method includes a method in which an oxide shell is first formed in the semiconductor crystal core by the sol-gel method or the like, and then an organic ligand is bonded, and a method in which an organic ligand coexists during the reaction of forming the oxide shell. The formation reaction of the oxide shell suitable for the latter method is the sol-gel method using metal alkoxides as raw materials. As a method utilizing the particularly preferred sol-gel method, a metal alkoxide containing an amino group, a hydroxyl group, a mercapto group, a carboxyl group, an acryloyl group, a methacryloyl group, or an epoxy group in a molecular structure, Mainly composed of semiconductor crystals and having a number average particle size of 1 to 50
An example is a method that requires a step of bonding to ultrafine particles having a size of nm. The term "ultrafine particles mainly composed of semiconductor crystals and having a number average particle diameter of 1 to 50 nm" as used herein means core-shell type semiconductor ultrafine particles in which an oxide shell has already been formed, or semiconductor ultrafine particles in the process of forming an oxide shell. Means
From the viewpoint of reactivity with the resin matrix and chemical stability of the resin composition, the functional group contained in the metal alkoxide is preferably an amino group, a methacryloyl group and an epoxy group, of which the amino group is most suitable. is there.

[Resin Composition Molded Product] The resin composition molded product of the present invention is mainly composed of the above resin composition, retains its characteristics, and has an average birefringence per 1 mm of optical path length of 10 n.
m or less. The term "average" as used herein means a value obtained by converting the measured value of birefringence in at least 10 arbitrary points of a given molded product into a value per 1 mm of optical path length by proportional calculation based on the optical path length in the measurement. Therefore, it is desirable that the number of measurement points is as large as possible in terms of reliability of the average value. If the average of the birefringence is too large, the optical strain of the resin composition molded product of the present invention may be too large to hinder the use as an optical member. Therefore, the average value of the birefringence is preferably 5 nm. Or less, more preferably 3 nm or less, and most preferably 2 nm. The measurement of such birefringence may be carried out with a commercially available birefringence meter, and the permissible range of the measurement temperature condition is 20 to 25 ° C.

The minimum thickness of the resin composition molded product of the present invention is usually 0.1 mm, and if it is too small, the mechanical strength of the resin composition molded product may be extremely reduced. Therefore, this minimum thickness is preferred. It is 0.5 mm, more preferably 1 mm. In addition, the maximum thickness of the resin composition molded body of the present invention is usually 200 mm, and if this is too large, the light transmittance as a whole of the resin composition molded body may extremely decrease, so this maximum thickness is preferably It is about 100 mm, more preferably about 50 mm.

There are no particular restrictions on the dimensions of the resin composition molded article of the present invention, but the characteristics of the resin composition of the present invention are transparency, light resistance, low water absorption and low optical distortion, and comparison with inorganic glass. Due to various characteristics of the transparent resin material, such as lightness and impact resistance, which are general characteristics of the transparent resin material, the resin composition molding of the present invention can be performed in a relatively large area thin-walled molded body application (for example, a display panel having an area of 50 cm ² or more). The utility value of the body increases. For example, in the case of a relatively small area such as a liquid crystal display panel of a mobile phone, it is possible to compensate for the poor impact resistance of the glass panel by the structural design of the entire device, but in a relatively large area such as a laptop computer. This is because the impact resistance design has a limit in applications using the panel.
Therefore, the resin composition molded body of the present invention preferably has a thickness of 0.1 mm to 50 mm, an area of preferably 50 to 50,000 cm ² , and more preferably 100 to 20.
000cm ^2, more preferably 200～10000Cm ²
Is. If this area is too large, even if the method for producing a resin composition molded article of the present invention is adopted, the optical strain increases due to deterioration of releasability from a molding die (mold etc.) and increase of birefringence. Or, if an attempt is made to reduce such optical distortion, the molding cycle may become extremely long.

The above-mentioned resin composition molded article retains the above-mentioned description regarding the physical properties, characteristics, composition and the like of the resin composition of the present invention as it is, and the preferable range and measuring method thereof are also the same as above. The resin composition molded body of the present invention,
Immerse in 40 ° C warm water for 1 hour and then 23 ° C relative humidity 5
It is desirable that the dimensional change rate before and after the warm water test in which it is allowed to stand in a 0% air atmosphere for 1 week is 0.05% or less. The dimensional change rate here is an arithmetic mean of dimensional change rates in two arbitrary orthogonal directions actually measured in a given resin composition molded body. For example, when a flat molded body is given, two straight lines that are orthogonal to each other are set on the flat surface, and then arbitrary line segments whose lengths can be measured are set on each of the straight lines (usually marked by ink or uneven marking. ), The length change of each line segment before and after the heating test is measured, and the arithmetic mean is calculated using the value obtained by dividing the length change by the length of the corresponding line segment before the heating test.

The hot water test is set in consideration of the hot water treatment conditions when manufacturing the panel. That is,
The above-mentioned molded body is washed with hot water a plurality of times before forming pixels, before forming transparent electrodes, and after forming an alignment film during panel manufacturing. This washing is usually performed with hot water at 40 ° C. for several minutes to several hours. There is. And about the condition of leaving still at 23 ° C. for 1 week in the air, as a representative example of the storage condition of the resin molded body in these washing steps, and JIS K-7
The value was set as 100. The permissible ranges of the temperature, relative humidity and time conditions in the hot water test are ± 2 ° C., ± 5% relative humidity and ± 5 minutes, respectively. Therefore, if the dimensional change rate before and after the hot water test is too large, it may hinder precision optical member applications, so it is preferably 0.03% or less, more preferably 0.01% or less.

Although the reason why the above-mentioned dimensional stability is obtained is not clear, the effect that the polymer chains of the resin matrix are adsorbed on the surface of the semiconductor ultrafine particles is very unprecedented by the use of the ultrafine particles having the above-mentioned specific particle size. It is presumed that due to the large surface area, it becomes noticeable at all, which may be related to the suppression of the mobility of the polymer chains as a whole of the molded body.

Although there is no limitation on the method for producing the above resin composition molded article, a preferred method is to produce a thermoplastic resin composition containing ultrafine particles by melting and shaping with a mold or the like. "Thermoplastic molding method"), and a polymerizable liquid mixture containing a polymerizable monomer and ultrafine particles are charged into a molding die, and then a polymerization reaction is performed to form a resin composition in the molding die. An example of such a method (hereinafter referred to as "crosslinked resin molding method") is used. Such a manufacturing method will be described in detail later.

The linear expansion coefficient of the resin composition molded product of the present invention is usually 6 × 10 ⁻⁵ / ° C. or less. The smaller this value is, the more the thermal stability of the dimension is improved, which is suitable for application to an optical member. Therefore, it is preferably 4 × 10 ^-5 / ° C or less, more preferably 3 × 10 ^-5 / ° C or less. . Since the semiconductor ultrafine particles are inorganic substances having a linear expansion coefficient smaller than that of the resin matrix, the linear expansion coefficient of the resin composition molded product of the present invention decreases as its content increases.

In the resin composition molded product of the present invention, it is desirable that the standard deviation of the directional anisotropy of the linear expansion coefficient measured as the whole of the molded product is 10% or less of the average of the linear expansion coefficient. The measurement of the coefficient of linear expansion here is performed by a commercially available thermomechanical analysis (TMA) device. In the measurement of the standard deviation of the directional anisotropy of the linear expansion coefficient, the arithmetic mean of the measured values of the linear expansion coefficient in at least 6 arbitrary directions of a given molded body is calculated as the average of the linear expansion coefficient. It is desirable that the number of measurement directions is as large as possible in terms of numerical reliability. If the standard deviation of the directional anisotropy of the linear expansion coefficient is too large, the dimensional stability of the resin composition molded product of the present invention may be insufficient as an optical member. Therefore, the value of the standard deviation is preferably 7 % Or less, more preferably 5
% Or less.

In the resin composition molded product of the present invention, it is desirable that the average of the surface roughness Ra be 0.1 μm or less. This Ra value is measured by a commercially available surface roughness measuring device (for example, using a diamond stylus (1 μmR, 90 ° cone)). If the Ra value is too large, for example, when used as a liquid crystal display element member, a problem such as color bleeding may occur and the image quality may be deteriorated, which may deteriorate the performance as an optical member. Or less, more preferably 0.01 μm or less.

When the resin composition which is the main component of the resin composition molded article of the present invention is a thermoplastic resin composition, it can be manufactured by the thermoplastic molding method described later and the productivity is improved, which is preferable. On the other hand, when the resin composition which is the main component of the resin composition molded body of the present invention is a crosslinked resin composition, it is preferable because the above-mentioned dimensional stability, heat resistance, and solvent resistance are improved. . The different characteristics of these two resin compositions are selected according to the application. The latter is characterized by improved dimensional stability, heat resistance, and solvent resistance. Since the resin matrix is a cross-linked resin, macroscopic deformation caused by changes in the entangled state of polymer chains due to external stress or heat It is presumed that this is due to the crosslinking effect that is significantly suppressed by the crosslinking points in the crosslinked resin matrix. The method for producing such a crosslinked resin composition is not limited, but it is preferably obtained by polymerizing a polymerizable liquid mixture containing a polymerizable monomer described below.

The semiconductor ultrafine particles contained in the resin composition molded product of the present invention are inorganic substances having optical characteristics different from those of the resin matrix which is an organic substance. It may have a feature of having a balance between the rate and the Abbe number.
Such a unique balance between the refractive index and the Abbe's number may be useful in applications where it is desirable to use the refraction of light such as a lens and a prism and to have a small birefringence. This is a case where the constant term C of the following mathematical formula (B) representing the relationship between the refractive index n _D and the Abbe number ν _D measured at ° C deviates from the range of 1.70 to 1.90.

[0043]

In Equation 2] _{n D = -0.005ν D + C (} B) a transparent resin material, generally tend to be birefringent increases as the optical path length is increased. However, when the above-mentioned semiconductor ultrafine particles are dispersed in a resin matrix, there may be a feature that the rate of increase in birefringence becomes smaller than ever in comparison with the increase in optical path length. Therefore, in a relatively thick molded product having a thickness of 0.1 mm or more like the resin composition molded product of the present invention, such a feature is advantageous in terms of lowering the birefringence.

Various additives may be used in combination with the resin composition molded product of the present invention unless the object of the present invention is significantly deviated. Examples of such additives are the same as those described in the resin composition. In the resin composition molded product of the present invention, the addition amount of these various additives is appropriately set according to the application, but is usually 10% by weight or less, preferably 5% by weight or less.
It is less than or equal to wt.

A coating layer such as a gas barrier layer, a hard coat layer or a conductive layer can be provided on the surface of the resin composition molded body of the present invention. Specific examples of the coating include a transparent conductive layer made of an inorganic oxide coating layer (for example, indium tin oxide which is an abbreviation ITO), a gas barrier layer (for example, silica), a gas barrier layer made of an organic coating layer, a hard coat, and the like. As the coating method, known coating methods such as a vacuum vapor deposition method, a CVD method, a sputtering method, a dip coating method and a spin coating method can be used. Adhesive layers may be used to enhance adhesion. The thickness of these coating layers is not limited, but is usually 100 μm or less, preferably 50 μm or less.

[Thermoplastic Resin Composition] A thermoplastic resin can be used as the resin matrix of the resin composition or the resin composition molded article of the present invention. The type of such a thermoplastic resin is not limited as long as the above-mentioned transparency condition is satisfied, and contains a crosslinked polymer component as long as it retains thermoplasticity (a property that it is softened by heating and can be shaped). Good. Preferred as such a thermoplastic resin is one having a light transmittance of 70% or more, preferably 80% or more, and more preferably 85% or more in accordance with the ASTM D-1003 (3 mm thickness) standard.

The above-mentioned thermoplastic resins are exemplified below, but any number of different kinds of thermoplastic resins may be mixed and used as long as the above-mentioned light transmittance is satisfied. Styrene resin
.. A homopolymer of a styrene derivative or a copolymer resin of a styrene derivative as a main component and a vinyl compound copolymerizable therewith. Examples of the styrene derivative include aromatic vinyl compounds such as styrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene and vinylnaphthalene. A rubber component may be allowed to coexist when the aromatic vinyl compound is polymerized.
The method for producing the styrene resin is not particularly limited, and conventionally known bulk polymerization, suspension polymerization, bulk-suspension polymerization,
It can be produced by radical polymerization by any polymerization method such as emulsion polymerization. As a typical styrene resin,
Examples thereof include polystyrene (PS resin), poly (α-methylstyrene), styrene-acrylonitrile copolymer (SAN resin), and styrene-methyl methacrylate copolymer, which may be used alone or in combination of two or more. Good.
The molecular weight of the styrene resin used in the present invention is not particularly limited, and the melt index is usually selected in the range of 0.5 to 25, and particularly preferably in the range of 5 to 20.

Acrylic resin: acrylic acid or its ester, methacrylic acid or its ester, acrylamide, methacrylamide, acrylonitrile,
It is a homopolymer or copolymer of an acrylic acid derivative such as methacrylonitrile. Such acrylic acid derivatives are described in, for example, Volume 16 of "Plastic Materials Course" published by Nikkan Kogyo Shimbun. Typical examples include methyl acrylate, ethyl acrylate, butyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, norbornane methyl methacrylate, norbornene methyl methacrylate, methacrylic acid. Examples thereof include adamantyl, benzyl methacrylate, hydroxyethyl methacrylate, phenyl methacrylate, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile. There is no particular limitation on the production method of the acrylic resin, conventionally known bulk polymerization, suspension polymerization,
It can be produced by radical polymerization by any polymerization method such as emulsion polymerization. Representative acrylic resins include polymethylmethacrylate (PMMA), polycyclohexylmethacrylate (PCHM), polyethylacrylate, methylmethacrylate-cyclohexylmethacrylate copolymer, and the like, which may be used alone or in combination. May be used in combination. The molecular weight of the acrylic resin used in the present invention is not particularly limited, and usually has a melt index of 1 to
It is selected in the range of 20 and particularly preferably in the range of 5 to 15.

Aromatic polycarbonate resin: one or more kinds of bisphenols which may contain polyhydric phenols having a valence of 3 or more as a copolymerization component, and carbonic acid esters such as bisalkyl carbonate, bisaryl carbonate and phosgene It is a polymer produced by the reaction with. The method for producing the aromatic polycarbonate resin used in the present invention is not limited, and for example, (a) an organic metal capable of dissolving a polymer produced from an alkali metal salt of a bisphenol and a carbonic acid ester derivative active in nucleophilic attack as raw materials. An interfacial polymerization method of causing a polycondensation reaction at the interface between the solvent and the alkaline water,
(B) Pyridine method in which bisphenols and a carbonate derivative active in nucleophilic attack are used as raw materials for polycondensation reaction in an organic base such as pyridine, and (c) bisphenols and carbonate esters such as bisalkyl carbonate and bisaryl carbonate It may be produced by any conventionally known method such as a melt polymerization method in which and are used as raw materials and melt polycondensation. The aromatic polycarbonate resin may be used alone or in combination of two or more kinds. The molecular weight of the aromatic polycarbonate resin used in the present invention is not particularly limited, and is usually gel permeation chromatography (GP) in a tetrahydrofuran (THF) solvent at 40 ° C.
It is sufficient that the weight average molecular weight Mw is 15,000 or more as measured by C), using the monomolecular weight-dispersed polystyrene as a control. Considering toughness and moldability, 20,000
It is preferable to select in the range of -80,000, and most preferable is the range of 35,000 to 65,000.

Amorphous polyolefin resin: Obtained by coordination polymerization or radical polymerization of a hydrocarbon containing a carbon-carbon multiple bond. Hydrogenated polystyrene, poly (4-
Methyl-1-pentene), poly (3-methyl-1-butene), norbornene cycloolefin polymers obtained by hydrogenating double bonds of ring-opening metathesis polymers, and ethylene and norbornene hydrocarbon copolymer Coalescence (trade names such as Arton manufactured by JSR Co., or Zeonex manufactured by Nippon Zeon Co., Ltd.), polytetracyclododecenes, and copolymers mainly containing these structures (for example, hydrophilicity control by copolymerization of polar monomers) And the like).

Polyamide resin: A polymer containing an amide bond (-NHCO-) in the main chain and capable of being melted by heating,
Characterized by high gas barrier properties against oxygen, etc. The polyamide-based fat suitable for use in the present invention is preferably one which gives an amorphous molded product under ordinary molding conditions, specifically, a polyamide or terephthalic acid obtained from terephthalic acid and / or isophthalic acid and hexamethylenediamine. Acid and / or polyamide obtained from isophthalic acid, adipic acid and hexamethylenediamine, copolymerized polyamide containing 1,3-phenylenedioxydiacetic acid as a copolymerization component, copolymer containing dimerized fatty acid as a copolymerization component Examples include polymerized polyamide. The polyamide resin may be a single kind or a mixture of two or more kinds. The molecular weight of the polyamide resin is not particularly limited, but normally, one having a relative viscosity measured in concentrated sulfuric acid of 25 ° C. in the range of 0.5 to 5.0 is preferably used, and further, from the viewpoint of toughness and moldability. The preferred range is 0.8 to 4.0.

Aromatic polyester resin: A polyester having an aromatic ring in the molecular chain, which is obtained by a condensation reaction of a dicarboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. As the aromatic polyester resin suitable for use in the present invention, those which give an amorphous molded product are preferable, and specific examples thereof include polyethylene terephthalate and polyethylene naphthalate. These may be used alone or in combination of two or more. There is no particular limitation on the molecular weight of the aromatic polyester used in the present invention, and it is preferable to use a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1: 1 at a concentration of 1 g / dL and an intrinsic viscosity measured at 30 ° C. [Η] is in the range of 0.5 to 3.0 dL / g. If the intrinsic viscosity is lower than this range, the toughness is extremely lowered, and if it is higher than this range, the melt viscosity is too high and molding is hindered, which is not preferable.

Polyphenylene ether resin: A polymer in which benzene ring residues are linked via an ether bond and can be melted by heating. These are polymers produced from a phenol or a reactive derivative thereof as a raw material by a known method, for example, oxygen using an oxidative coupling catalyst, or oxidative coupling polymerization with an oxygen-containing gas. Specific examples of the phenols and the polymerization catalyst are described in detail, for example, in Japanese Patent Application Laid-Open No. 4-239029, and as typical phenols, phenol,
Methylphenols such as o-cresol, 2,6-xylenol, 2,5-xylenol, 2,3,6-trimethylphenol and the like can be mentioned, and these phenols can be used alone or in combination of two or more kinds. .
The most common polyphenylene ether resin includes poly (2,6-dimethyl-1,4-phenylene) ether or a copolymer having this as a main structure.
The polyphenylene ether resin may be used alone or in combination of two or more kinds. The molecular weight of the polyphenylene ether resin used in the present invention is not particularly limited, and is usually 0.6
The intrinsic viscosity [η] of a chloroform solution having a concentration of g / dL at 25 ° C. is selected within the range of 0.2 to 0.6 dL / g, and 0.35 to 0.55 dL / g from the viewpoint of toughness and moldability. It is preferable to select within the range.

Polyarylene sulfide resin: A polymer in which an aromatic residue is bonded via a thioether bond and can be heated and melted. Specific examples of such a polymer structure and a production method are described in detail, for example, in JP-A-5-194851. The main chain structure preferably used in the present invention has the following formula, that is,-(-S-Φ-) _n- ,
[In formula, (phi) is a phenylene group and n is a natural number which means repetition of each structure. ] And a polyphenylene sulfide having a repeating unit of the following formula, namely,-(-S-Φ
_{-) m - (- SO 2} -Φ-) n -, [ wherein, [Phi is a phenylene group, m and n are natural numbers, meaning the repetition of the structure, each of the repeating units represented by m and n May be a random array or an array forming a block. ] It is a polyphenylene sulfide sulfone having a repeating unit of. These may be used alone or in combination of two or more. The molecular weight of the polyarylene sulfide-based resin used in the present invention is not particularly limited and can be usually selected in the range of 10,000 to 500,000 in terms of weight average molecular weight. From the viewpoints of toughness and moldability, a range of 30,000 to 300,000 is preferable, but a high molecular weight one that easily gives an amorphous molded body may be preferable. This weight average molecular weight can be determined by gel permeation chromatography (GPC). For example, in the case of polyphenylene sulfide, 1-chloronaphthalene can be used as a developing solvent.

Of these examples, the repeating unit having a high molecular structure such as styrene resin, acrylic resin, aromatic polycarbonate resin, and amorphous polyolefin resin is preferably selected from hydrogen, carbon, and oxygen. Among them, the acrylic resin, the aromatic polycarbonate resin and the amorphous polyolefin resin are more preferable in terms of mechanical strength, and the aromatic polycarbonate resin and the amorphous polyolefin resin are It is more preferable in terms of heat resistance, and the amorphous polyolefin resin is most preferable in terms of low water absorption.

Reaction with any of the functional groups which are preferable functional groups of the organic ligand to which the semiconductor ultrafine particles are bound, such as amino group, hydroxyl group, mercapto group, carboxyl group, acryloyl group, methacryloyl group and epoxy group. In view of the property, the preferable resin matrix is such that the polymer constituting the resin matrix has any functional group of ester bond, amide bond, carbonate bond, urethane bond, urea bond and carbon-carbon double bond as described above. Since it is contained in the polymer structure, preferable thermoplastic resins satisfying such conditions include acrylic resins, aromatic polycarbonate resins, and amorphous polyolefin resins having an ester group in the polymer side chain (for example, JSR). Amorphous polyolefin resin, which is the trade name Arton supplied by the company).

[Polymerizable Liquid Mixture and Polymerizable Monomer] When a crosslinked resin composition is used as the resin matrix of the resin composition molding of the present invention, the type of crosslinked resin forming the main body of the resin matrix is There is no limitation as long as the transparency condition is satisfied. The raw material of such a crosslinked resin is usually a polymerizable liquid mixture containing a polymerizable monomer having two or more polymerizable functional groups in the molecule as an essential component.

Such a polymerizable liquid mixture may contain a polymerizable monomer having one polymerizable functional group in the molecule, and as long as it does not significantly impair the polymerizability of the above polymerizable monomer. You may contain the liquid (solvent) which does not have polymerizability. Also. Usually, it is preferable to add a polymerization initiator. As such a polymerization initiator, a photoradical generator which is a compound having a property of generating a radical by light and a thermal radical generator which is a compound having a property of generating a radical by heat are general, and such known compounds are known. Can be used. Preferred polymerization initiator is a photoradical generator from the viewpoint that homogeneity of progress of the polymerization reaction and heating are not always required, and as such a photoradical generator, benzophenone, benzoin methyl ether, benzoin isopropyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone,
2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like are exemplified, and a plurality of kinds may be used in combination. Of these, preferred are 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzophenone. The amount of the polymerization initiator added is usually 0.001 to 3 parts by weight, preferably 0.01 to 1 part by weight, and more preferably 0.02 to 0.3, based on 100 parts by weight of the total amount of the polymerizable monomers. It is parts by weight, and if the addition amount is too large, the polymerization reaction may rapidly progress to bring about an increase in birefringence as well as deteriorate the hue, and if it is too small, it may not be possible to sufficiently cure. is there.

As the polymerizable monomer having two or more polymerizable functional groups in the above-mentioned molecule, a crosslinked resin composition having excellent transparency and low birefringence is provided, so that it has a functionality of two or more (meta). Acrylates are preferably used. However, the expression "(meth) acrylate" here means either acrylate or methacrylate. Specifically, triethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, 2,2
-Bis [4- (meth) acryloyloxyphenyl] propane, 2,2-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] propane, bis (oxymethyl) tricyclo [5.2.1.0] ^2,6 ] decane dimethacrylate, p-bis [β- (meth) acryloyloxyethylthio] xylylene, 4,4′-bis [β-
(Meth) acryloyloxyethylthio] diphenylsulfone and other divalent (meth) acrylates, trimethylolpropane tris (meth) acrylate, glycerin tris (meth) acrylate, pentaerythritol tris (meth) acrylate and other trivalent ( Examples thereof include tetravalent (meth) acrylates such as (meth) acrylates and pentaerythritol tetrakis (meth) acrylate, and indeterminate polyvalent (meth) acrylates such as urethane acrylate and epoxy acrylate. Among these, the divalent (meth) acrylates are preferably used because of the controllability of the crosslinking formation reaction.

Of the above-exemplified (meth) acrylates, it is particularly preferable to achieve transparency and low birefringence of the resulting polymer in a well-balanced manner. Is in use. Component A is bis (meth) having an alicyclic skeleton represented by the following general formula (1).
It is an acrylate.

[0061]

[Chemical 3]

In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or a methyl group, R ^c and R ^d are each independently an alkylene group having 6 or less carbon atoms, and x is 1 or 2, and y represents 0 or 1. Specific examples of the component A represented by the general formula (1) include bis (hydroxymethyl) tricyclo [5.
2.1.0 ^2,6 ] decane = diacrylate, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate, bis (hydroxymethyl) tricyclo [5.2.1. 0 ^2,6 ] decane acrylate methacrylate and mixtures thereof, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^9,13 ] Pentadecane diacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 .
0 ^9,13 ] pentadecane dimethacrylate, bis (hydroxymethyl) pentacyclo [6.5.1.1 ^3,6 . 0
^2,7 . 0 ^9,13 ] Pentadecane acrylate methacrylate and mixtures thereof. These tricyclodecane compounds and pentacyclodecane compounds are
You may use together multiple types.

Component B is a bis (meth) acrylate having a sulfur atom represented by the following general formula (2).

[0064]

[Chemical 4]

However, in the general formula (2), R ^a and R ^b are the same as in the case of the general formula (1), and R ^e represents an alkylene group having 1 to 6 carbon atoms. Each Ar represents an arylene group or an aralkylene group having 6 to 30 carbon atoms, and these hydrogen atoms may be substituted with a halogen atom other than fluorine. Each X represents an oxygen atom or a sulfur atom, and when all X are oxygen atoms, at least one of the Ys is a sulfur atom or a sulfone group (-SO ₂
-), When at least one of each X is a sulfur atom,
Each Y is a sulfur atom, a sulfone group, a carbonyl group (-CO-), and an alkylene group having 1 to 12 carbon atoms,
Represents an aralkylene group, an alkylene ether group, an aralkylene ether group, an alkylene thioether group or an aralkylene thioether group, j and p each independently represent an integer of 1 to 5 and k represents an integer of 0 to 10. . When k is 0, X represents a sulfur atom.

Specific examples of the component B represented by the general formula (2) include p-bis [β- (meth) acryloyloxyethylthio] xylylene and m-bis [β- (meth) acryloyloxyethylthio. ] Xylylene, α, α′-
Bis [β- (meth) acryloyloxyethylthio]-
2,3,5,6-tetrachloro-p-xylylene, 4,
4′-bis [β- (meth) acryloyloxyethoxy] diphenyl sulfide, 4,4′-bis [β- (meth) acryloyloxyethoxy] diphenylsulfone, 4,4′-bis [β- (meth) acryloyloxy Ethylthio] diphenyl sulfide, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl sulfone, 4,4′-bis [β- (meth) acryloyloxyethylthio] diphenyl ketone, 2,4 ′
-Bis [β- (meth) acryloyloxyethylthio]
Diphenyl ketone, 5,5′-tetrabromodiphenyl ketone, β, β′-bis- [p- (meth) acryloyloxyphenylthio] diethyl ether, β, β′-bis- [p- (meth) acryloyloxyphenyl Thio]
Examples thereof include diethyl thioether, and these may be used in combination of plural kinds. Among these, bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane dimethacrylate has excellent transparency and heat resistance and is particularly preferably used.

The ratio of the polymerizable monomer having two or more polymerizable functional groups in the molecule to the total amount of the polymerizable monomers contained in the above polymerizable liquid mixture is usually 0.1 to 100 mol%.
In view of dimensional stability and mechanical strength of the crosslinked resin composition produced by the polymerization reaction, the lower limit value is preferably 1 mol%, more preferably 3 mol%. Various additives may be added to the polymerizable liquid mixture as long as the molded resin composition molded article does not significantly deviate from the object of the present invention. Examples of such additives include antioxidants, heat stabilizers, or stabilizers such as light absorbers, glass fibers, glass beads, mica, talc, kaolin, clay minerals, metal fibers, fillers such as metal powder, Carbon materials such as carbon fiber, carbon black, graphite, carbon nanotubes, fullerenes such as C ₆₀ , antistatic agents, plasticizers, release agents, defoamers, leveling agents, antisettling agents, surfactants, and thixotropy Modifiers such as agents, pigments, dyes,
Illustrative examples include colorants such as hue adjusters.

Regarding the method for producing the above-mentioned polymerizable liquid mixture, the constituent component thereof, that is, the polymerizable monomer having two or more polymerizable functional groups in the molecule represented by the general formula A and / or B, The above ultrafine particles and additional components used as necessary (a polymerizable monomer having one polymerizable functional group in the molecule, a liquid having no polymerizability, the above polymerization initiator, or the above various additives). Etc.) are mixed and carried out. Such mixing can be carried out by using a known mixing device which may have a mechanical stirring device, and if necessary, such as light shielding, cooling, and inert atmosphere of the purpose of controlling the polymerization initiation behavior. You may use together.

[Semiconductor Crystal] A semiconductor crystal has electromagnetic wave absorption (hereinafter simply referred to as “absorption” unless otherwise specified) and high refractive index according to the energy difference (band gap) between the valence band and the conduction band. Since it has characteristics, it is particularly useful as a constituent material of the ultrafine particles. Further, the quantum effect becomes noticeable by setting the grain size to about 10 nm or less, the energy levels are separated from each other by the quantization of the energy levels, and they are a function of the crystal grain size. Be controlled. In such semiconductor nanocrystals, the fundamental absorption of semiconductor crystals (Fundam
The exciton (E) that appears in the energy region slightly lower than the absorption edge on the long wavelength side of the optical absorption
The xciton (exciton) absorption band has not only a very small energy width, but also the exciton level is isolated from the conduction band level and the interaction probability with an adjacent energy level is relatively small.

By using ultrafine particles containing a semiconductor crystal having a light emitting property, the resin composition and the resin composition molded product of the present invention are also useful for applications utilizing such a light emitting property. In particular, light emission from the exciton level is excellent in color purity because the line width of the emission band is small, and since the emission wavelength can be controlled by the grain size of the semiconductor crystal by the quantum effect, it is particularly useful. is there. Further, the feature of the exciton absorption band is applied to, for example, a super-resolution technique for effectively narrowing the incident light beam diameter on an optical disk to achieve high density recording by utilizing the light absorption saturation characteristic in the absorption band. can do.

The composition of the semiconductor crystal used in the present invention is
There is no particular limitation, but specific composition examples are element symbols or
As an example of the composition formula, the composition of C, Si, Ge, Sn, etc.
Periodic Table 1 of Periodic Table Group 14 elements, P (black phosphorus), etc.
Group 5 element simple substance, such as Se and Te
A simple substance or a plurality of periodic table group 14 elements such as SiC
Compound, SnO₂, Sn (II) Sn (IV) S₃, SnS₂, Sn
S, SnSe, SnTe, PbS, PbSe, PbTe
Of elements of Group 14 of the periodic table and elements of Group 16 of the periodic table
Objects, BN, BP, BAs, AlN, AlP, AlAs,
AlSb, GaN, GaP, GaAs, GaSb, In
Periodic table group 13 elements such as N, InP, InAs, InSb
A compound of an element and a Group 15 element of the periodic table (or III-V
Group compound semiconductor), Al₂S₃, Al₂Se₃, Ga₂S₃,
Ga₂Se₃, Ga₂Te₃, In₂O₃, In₂S₃, In₂
Se₃, In₂Te₃Periodic table group 13 elements such as
Compounds with Group 16 elements, TlCl, TlBr, TlI, etc.
Of periodic table group 13 elements with periodic table group 17 elements
Thing, ZnO, ZnS, ZnSe, ZnTe, CdO, C
dS, CdSe, CdTe, HgS, HgSe, HgT
Conversion of elements of group 12 of the periodic table such as e to elements of group 16 of the periodic table
Compound (or II-VI group compound semiconductor), As ₂S₃, A
s₂Se₃, As₂Te₃, Sb₂S₃, Sb₂Se₃, Sb₂
Te₃, Bi₂S₃, Bi₂Se₃, Bi₂Te₃Periodic table of etc.
Cu, a compound of a Group 15 element and a Group 16 element of the periodic table₂
O, Cu₂Periodic Table Group 11 elements such as Se and Periodic Table 16th
Compounds with group elements, CuCl, CuBr, CuI, Ag
Periodic Table Group 11 elements such as Cl and AgBr and Periodic Table 17
Group 10 elements such as NiO, etc.
Periodic table of compounds with group 16 elements, CoO, CoS, etc.
Compounds of Group 9 elements of the periodic table and Group 16 elements of the periodic table, α-F
e₂O₃, Γ-Fe₂O₃, Fe₃O_FourIron oxides such as FeS
Of periodic table group 8 elements such as
And periodic table group 7 elements such as MnO
Compound with, MoS₂, WO₂Periodic Table Group 6 elements such as
Compounds with Group 16 elements, VO, VO₂, Ta₂O_Five
Of periodic table group 5 element and other periodic table group 16 element
Thing, TiO₂, Ti₂O_Five, Ti₂O₃, Ti_FiveO₉Oxidation of etc.
Titanium (Crystal type is rutile type, rutile / anatase mixture)
Crystal type or anatase type is acceptable), ZrO₂
Of periodic table group 4 elements and other periodic table group 16 elements
Thing, Y₂O₃, La₂O₃, Ce₂O₃Periodic Table Group 3 elements such as
(Including lanthanoid elements) and elements of Group 16 of the periodic table
Periodic Group 2 elements such as compounds, MgS, MgSe, etc.
Table Compounds with Group 16 elements, CdCr₂O_Four, CdCr₂
Se_Four, CuCr₂S_Four, HgCr₂Se_FourChalcogen, etc.
Spinels or BaTiO₃Etc. Na
Oh, G. Schmid et al .; Adv. Mater. , 4
Vol., P. 494 (1991) (BN).₇₅
(BF₂)₁₅F₁₅, D. Fenseke et al .; Ange
w. Chem. Int. Ed. Engl. , Volume 29, 1
Cu reported on page 452 (1990)₁₄₆Se₇₃
(Triethylphosphine)_{twenty two}The structure is fixed like
The semiconductor clusters that are present are also exemplified.

Of these, those practically important are, for example, SnO ₂ , SnS ₂ , SnS, SnSe, SnTe, P.
Compounds of periodic table group 14 element and periodic table group 16 element such as bS, PbSe, PbTe, GaN, GaP, GaA
s, GaSb, InN, InP, InAs, III-V group compound semiconductor such as _{InSb, Ga 2 O 3, Ga} 2 S 3, Ga 2
Se ₃ , Ga ₂ Te ₃ , In ₂ O ₃ , In ₂ S ₃ , In ₂ S
e ₃ and In ₂ Te ₃ etc. Periodic Table Group 13 elements and Periodic Table 1
Compounds with Group 6 elements, ZnO, ZnS, ZnSe, Zn
Te, CdO, CdS, CdSe, CdTe, HgO,
II-VI group compound semiconductors such as HgS, HgSe, and HgTe, As ₂ O ₃ , As ₂ S ₃ , As ₂ Se ₃ , As ₂ Te ₃ , and S.
b ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi
₂ O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , Bi ₂ Te ₃ and other compounds of periodic table group 15 element and periodic table group 16 element, α-Fe
₂ O ₃ , γ-Fe ₂ O ₃ , iron oxides such as Fe ₃ O ₄ and compounds of periodic table group 8 element such as FeS and periodic table group 16 element,
Compounds of elements of Group 4 of the periodic table and elements of Group 16 of the periodic table such as the above-mentioned titanium oxides and ZrO ₂ , Y ₂ O ₃ , La ₂ O ₃ and C
It is a compound of an element of Group 3 of the periodic table (including a lanthanoid element) such as e ₂ O ₃ and an element of Group 16 of the periodic table.

Among these, SnO ₂ , GaN, Ga
P, In ₂ O ₃ , InN, InP, Ga ₂ O ₃ , Ga ₂ S ₃ ,
In ₂ O ₃ , In ₂ S ₃ , ZnO, ZnS, CdO, Cd
S, the above iron oxides, rutile-type and anatase-type titanium dioxide, ZrO ₂ , Y ₂ O ₃ , Ce ₂ O ₃ , MgS, etc. do not contain highly toxic negative elements, so they are resistant to environmental pollution and are safe against living organisms. From the standpoint of properties, SnO ₂ , In
_A composition containing no highly toxic positive element such as ₂ O ₃ , ZnO, ZnS, α-Fe ₂ O ₃ , rutile type or anatase type titanium dioxide, ZrO ₂ , Y ₂ O ₃ and Ce ₂ O ₃ is more preferable.

Metal oxide semiconductor crystals such as ZnO, α-Fe ₂ O ₃ , rutile type or anatase type titanium dioxide, and Ce ₂ O ₃ are light absorbing, have a high refractive index, are safe and are inexpensive. It is most preferable for applications such as ultraviolet absorbing materials and high refractive index coatings. In addition, colored semiconductor crystals having absorptivity in the visible region, such as iron oxides such as α-Fe ₂ O ₃ are important for coloring materials such as pigments.

The most preferable semiconductor crystals for the purpose of making the resin composition molded article of the present invention almost colorless and transparent and exhibiting excellent ultraviolet absorbing ability are the above-mentioned titanium oxides (typically rutile type or anatase type titanium dioxide). ), ZnO
And Ce ₂ O ₃ . On the other hand, in the case of utilizing the light emitting ability of the semiconductor crystal, G having an emission band in the visible region and its vicinity
III-V such as aN, GaP, GaAs, InN, InP
Group compound semiconductor, ZnO, ZnS, ZnSe, ZnT
e, CdO, CdS, CdSe, CdTe, HgO, H
II-VI group compound semiconductors such as gS, In ₂ O ₃ , In ₂ S _{3 and the} like are important, and among them, ZnO, ZnS, ZnSe, ZnT are preferable because of the controllability of the grain size of the semiconductor crystal and the light emitting ability.
II-VI group compound semiconductors such as e, CdO, CdS, CdSe, and particularly ZnO, ZnS, ZnSe, CdS, C
dSe and the like are more preferably used for this purpose.

In any of the semiconductor crystals exemplified above, for example, Al, V, Cr, Mn, Co, C as a slight amount of doping element (meaning impurities intentionally added) is added as necessary.
u, Sb, W, Zn, Zr, Ag, Pt, Cl, Ce,
Eu, W, Hg, Pb, Bi, Eu, Tb, Dy, E
Elements such as r and Sm may be added. For example, Y ₂ O ₃
By adding Eu to ZnS and adding Ag, Cu, Tb, Mn, or the like to ZnS, a phosphor having the doped element as a light emitting source can be obtained. Further, addition of an appropriate doping element such as Zr to the above titanium dioxide, ZnO and Ce ₂ O ₃ may have the effect of reducing the photocatalytic activity. The main effect of the doping element in the present invention is to chemically stabilize the resin composition such that the energy of electromagnetic wave absorption is dissipated by a phenomenon other than a chemical reaction such as light emission or heat generation to suppress or prevent decomposition degradation of the resin matrix. It is thought to be to improve the sex.

The semiconductor crystal in the present invention is, for example, A.
R. Kortan et al .; Am. Chem. Soc. ，
112, 1327 (1990) or US Pat.
As reported in Japanese Patent No. 985173 (1999), a so-called core-shell structure composed of an inner core (core) and an outer shell (shell) may be formed. Such a core-shell type semiconductor crystal may be suitable for applications using the exciton absorption / emission band. In this case, it is generally effective to form an energy barrier by using a semiconductor crystal composition of the shell having a band gap (band gap) larger than that of the core. It is presumed that this is due to a mechanism that suppresses the influence of an undesired surface level or the like due to the influence of the external environment or the crystal lattice defect on the crystal surface. The composition of the semiconductor crystal that is preferably used for such a semiconductor shell depends on the band gap of the core semiconductor crystal, but the band gap in the bulk state has a temperature of 30
Those having a voltage of 2.0 electron volts or more at 0 K, for example, BN, BAs, III-V group compound semiconductors such as GaN and GaP, ZnO, ZnS, ZnSe, ZnTe, CdO,
A II-VI group compound semiconductor such as CdS, a compound of an element of Group 2 of the periodic table and an element of Group 16 of the periodic table, such as MgS or MgSe, is preferably used. Among these, the semiconductor crystal composition which becomes a more preferable shell is II, such as BN, BAs, and GaN.
Group IV compound semiconductor, ZnO, ZnS, ZnSe, C
II-VI group compound semiconductor such as dS, compound having a group 2 element of the periodic table such as MgS, MgSe, etc. and group 16 element of the periodic table having a bulk band gap of 2.3 eV or more at a temperature of 300K And most preferable are BN, BAs, GaN, ZnO, ZnS, ZnSe, and M.
The band gap of gS, MgSe, etc. in the bulk state is 2.5 eV or more at a temperature of 300K,
ZnS is most preferably used in terms of chemical synthesis. When a combination example of particularly suitable core-shell composition is expressed by a composition formula,
CdSe-ZnS, CdSe-ZnO, CdSe-Cd
S, CdS-ZnS, CdS-ZnO, etc. are mentioned.

When utilizing the light absorption ability of the semiconductor crystal,
The absorption edge wavelength of the absorption spectrum is 300 to 600 nm
It is preferably within the range. The lower limit of the absorption edge wavelength range is more preferably 330 nm, further preferably 370 nm, for the purpose of absorbing the ultraviolet region that modifies the resin matrix, while the upper limit is more preferable in terms of transparency in the visible region. It is preferably 550 nm, more preferably 500 nm, and most preferably 450 nm.

[Manufacturing Method of Semiconductor Nanocrystal] The manufacturing method of the ultrafine particles of the semiconductor crystal (referred to as “semiconductor nanocrystal” in the present invention) is not limited, but the following three liquid phase methods are exemplified. . (1) A method of allowing a raw material aqueous solution to exist as a reverse micelle in a non-polar organic solvent and growing crystals in the reverse micelle phase (hereinafter referred to as "reverse micelle method"). S. Zou
Int. J. Quant. Chem. , Volume 72, 4
39 (1999). A method suitable for industrial production in that known reverse micelle stabilization technology can be used, a relatively inexpensive and chemically stable salt can be used as a raw material, and that it can be performed at a relatively low temperature not exceeding the boiling point of water. Is. However, the current state of the art may be inferior to the light emission characteristics as compared with the case of the hot soap method described below. (2) A method of injecting a thermally decomposable raw material into a high temperature liquid-phase organic medium to grow crystals (hereinafter referred to as "hot soap method"). E. B. Katari et al .; Phy
s. Chem. , 98, 4109-4117 (199
This is the method reported in 4). Semiconductor crystal particles excellent in particle size distribution and purity are obtained as compared with the reverse micelle method,
The product is characterized by excellent luminescence properties and is usually soluble in organic solvents. In order to desirably control the reaction rate in the process of crystal growth in the liquid phase in the hot soap method, a coordinating organic compound having an appropriate coordinating force for semiconductor constituent elements is used as a liquid phase component (solvent and organic ligand (Also serves as). Examples of such a coordinating organic compound include trialkylphosphines such as tributylphosphine and trioctylphosphine, trioctylphosphine oxide (hereinafter referred to as TOPO).
Abbreviated) and the like, and ω-aminoalkanes such as dodecylamine, tetradecylamine, hexadecylamine, octadecylamine and the like. Of these, trialkylphosphine oxides such as TOPO and ω such as hexadecylamine
-Aminoalkanes are preferably used. By such hot soap method, CdSe, CdS, ZnSe, Zn
II-VI group compound semiconductor nanocrystals such as S and ZnO, TiO
Oxide semiconductor nanocrystals such as ₂ and γ-Fe ₂ O ₃ can be synthesized with a number average particle size of about 3 to 8 nm. (3) A method suitable for industrial production in which a semiconductor crystal or a precursor thereof is generated at a relatively low temperature of about 100 ° C. or lower in a protic solvent such as water or ethanol by using an acid-base reaction as a driving force (hereinafter referred to as “sol. Generation method ”).
For example, the synthesis example of titanium oxide nanocrystals is Seijiro Ito et al.
Coloring Material, Vol. 57, No. 6, 305-308 (1984), a synthetic example of zinc oxide nanocrystals is described in L.A. Spanhel et al .;
Am. Chem. Soc. , 113, 2826 (1
991). Examples of suitable raw materials in the sol generation method include titanyl sulfate for the synthesis of titanium oxide nanocrystals, and zinc salts such as zinc acetate and zinc nitrate for the synthesis of zinc oxide nanocrystals. Metal alkoxides such as tetraethyl orthosilicate (abbreviation TEOS) and tetraisopropoxy orthotitanate can also be preferably used as a raw material. In particular, in the case of synthesizing oxide nanocrystals by a sol generation method, for example, as in the synthesis of titanium oxide nanocrystals using titanyl sulfate as a raw material, a precursor such as hydroxide is used, and then an acid or alkali (preferably Procedures for dehydration condensation or deflocculation of this (with an acid) to form a hydrosol are also possible. In the procedure via such a precursor, it is preferable in terms of purity of the final product to isolate and purify the precursor by an arbitrary method such as filtration or precipitation separation (centrifugation if necessary). To the hydrosol, a suitable surfactant such as sodium dodecylbenzene sulfonate (abbreviation DBS) or potassium 3-methacryloyloxypropane sulfonate is added,
The sol particles (that is, the nanoparticles of the semiconductor or its precursor) may be made water-insoluble and isolated.

When there are plural kinds of the semiconductor raw material, these may be mixed in advance, or they may be individually injected into the reaction liquid phase. These raw materials may be used as a solution using an appropriate diluting solvent. [Organic Ligand] When the semiconductor ultrafine particles used in the present invention have organic ligands compatible or reactive with the resin matrix bound thereto, the semiconductor ultrafine particles are dispersed in the resin matrix. In some cases, the properties are dramatically improved, and the resin composition or resin composition molded product of the present invention is improved in transparency, light resistance, dimensional stability, mechanical strength, and effective in reducing birefringence. The effect of such an organic ligand is an effect of suppressing aggregation of semiconductor ultrafine particles, an effect of improving compatibility with the resin matrix, or a chemical reaction between the organic ligand and a polymer constituting the resin matrix. It is considered that this is due to a combined effect such as the effect of bond formation by. The binding of the organic ligand may improve electromagnetic characteristics such as the light absorption and emission ability of the semiconductor ultrafine particles.

The molecular weight of the organic ligand used in the present invention is usually 100 to 900, more preferably 200 to 80.
0, more preferably 300 to 750. If this molecular weight is too large, various physical properties of the resin matrix, particularly mechanical properties (strength, elastic modulus, heat resistance, etc.) may be impaired.
Although the molecular weight may have a distribution, in view of the role of the organic ligand, the weight average molecular weight Mw and the number average molecular weight Mn are
The ratio Mw / Mn is usually 1 to 10, preferably 1 to 7, more preferably 1 to 5, and most preferably 1 to
It is preferable to control to 3.

The reactivity of the organic ligand with respect to the resin matrix mentioned above means that the organic ligand and the polymer constituting the resin matrix (whether a thermoplastic resin or a crosslinked resin) form a bond. It means reactivity to give a living condition. The following four methods can be considered to provide such a state. That is, the first is a chemical reaction between the organic ligand bound to the semiconductor ultrafine particles and the polymer constituting the resin matrix, and the second is the chemical reaction between the organic ligand bound to the semiconductor ultrafine particles and the polymer constituting the resin matrix. Reaction with a given polymerizable monomer (may be a copolymerization reaction with the polymerizable monomer) and subsequent polymerization reaction of the polymerizable monomer, and thirdly, an organic ligand and a resin matrix are constituted. Chemical reaction with the polymer and the subsequent bonding reaction between the organic ligand and the semiconductor ultrafine particles, and fourthly, the reaction between the organic ligand and the polymerizable monomer that gives the polymer forming the resin matrix ( It may be a copolymerization reaction with the polymerizable monomer), a polymerization reaction of the polymerizable monomer to be proceeded next, and a binding reaction of the organic ligand and the semiconductor ultrafine particles to be further advanced.

There is no limitation on the method of binding the organic ligand to the semiconductor ultrafine particles and the molecular structure of the organic ligand used for the method. It is represented by.

[0084]

Embedded image where X represents a functional group that forms an arbitrary chemical bond (for example, a covalent bond, an ionic bond, a coordinate bond, a hydrogen bond, etc.) with the surface of the semiconductor ultrafine particles, Y represents a functional group having compatibility or reactivity with the resin matrix, and R represents a divalent organic residue having 1 to 30 carbon atoms which connects X and Y.

The functional group X preferably forms a covalent bond or a coordinate bond with the surface of the semiconductor ultrafine particles to be used, most preferably a covalent bond. Specific examples of the functional group X include a metal alkoxide group which is an active functional group such as a silane coupling agent or a titanate coupling agent which has been conventionally used for surface treatment of oxides such as silica, alumina and titania, or following such a functional group containing a periodic table group 15 or 16 element, i.e., primary amino group (-NH _2), 2 amino groups (-NHR; provided that R is a methyl group, an ethyl group, a propyl group, A butyl group, a phenyl group, or another hydrocarbon group having 6 or less carbon atoms; the same applies hereinafter), 3
Primary amino group (-NR ¹ R ² ; however, R ¹ and R ² are independently a hydrocarbon group having 6 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group; the same applies hereinafter), Periodic Table 1 of nitrogen-containing functional groups such as pyridyl groups and amide bonds, phosphine groups, phosphine oxide groups, phosphoric acid groups, phosphorous acid groups, phosphorus-containing functional groups such as phosphine selenide groups, etc.
A functional group containing a Group 5 element, a hydroxyl group, a carboxyl group,
β-diketone group, oxygen-containing functional group such as β-diketonate group, mercapto group (or thiol group), sulfide bond, sulfoxide group, thioacid group (-COSH), dithioacid group (-CSH), sulfonic acid group, Examples thereof include functional groups containing a Group 16 element of the periodic table, such as a xanthate group, a xanthate group, an isothiocyanate group, a thiocarbamate group, and a sulfur-containing functional group such as a thiophene ring. Among these, preferably used are nitrogen-containing functional groups such as pyridyl groups and primary amino groups, phosphine derivative groups such as phosphine groups and phosphine oxide groups, and acidic groups such as phosphoric acid groups, carboxyl groups, and sulfonic acid groups. , A mercapto group and other sulfur-containing functional groups. Among these, the phosphine oxide group and the mercapto group are excellent in the binding force to the transition metal element contained in the semiconductor ultrafine particles, and the phosphoric acid group, the carboxyl group, the sulfonic acid group and other acidic groups are bonded to the oxide semiconductor crystal. It is most preferably used because of its excellent strength.

When the functional group Y is a functional group having reactivity with the resin matrix, nucleophilic or electrophilic substitution of hydroxyl group, amino group, mercapto group, carboxyl group, ester group, amide group, etc. Reactive functional group,
Acryloyl group, methacryloyl group, maleoyl group, vinylphenyl group, vinyl ester group, vinylamino group,
Examples thereof include radically polymerizable groups such as ethynyl group and functional groups having ring-opening reactivity such as aliphatic ether groups such as epoxy group and tetrahydrofuranyl group.

Among the examples of the above-mentioned functional group Y, the amino group is rich in a bond derived from a carboxyl group such as an ester bond, a carbonate bond, an amide bond and the like and has a nucleophilic substitution reactivity with an epoxy group. Resins containing a carbonate bond, an amide bond and an epoxy group (for example, an aromatic polyester resin, an aromatic polycarbonate resin, a polyamide resin, an epoxy resin, an ester bond, especially an acrylic resin having a methyl ester group in its side chain or an amorphous polyolefin resin) Etc.) is suitable for application to a resin matrix mainly composed of Further, a radical polymerizable group such as an acryloyl group, a methacryloyl group, a maleoyl group, a vinylphenyl group, a vinyl ester group, a vinylamino group, an ethynyl group is a polymerizable monomer or acetic acid which gives the styrene resin and the acrylic resin. Since it has a radical copolymerizability with an arbitrary radically polymerizable monomer such as vinyl, it is suitable for application to a resin matrix mainly composed of these two resins. Among the above radically polymerizable groups, acryloyl group, methacryloyl group, maleoyl group and vinylphenyl group are preferable in terms of radical polymerizability, and among them, acryloyl group, methacryloyl group and vinylphenyl group are further preferable, and radically polymerizable group. From the viewpoint of controllability, the methacryloyl group and vinylphenyl group are most preferable.

On the other hand, when the functional group Y is a functional group having compatibility with the resin matrix, its chemical structure is part or all of the chemical structure of the repeating unit of the polymer which is the main constituent of the resin matrix. Is preferably the same as or similar to. With respect to the number of carbon atoms of the divalent organic residue R, the mobility required to fully function the compatibility or reactivity of the functional group Y is secured, and the semiconductor ultrafine particles are protected from unfavorable chemical reactions from the outside world. Therefore, the lower limit is preferably 3 or more, more preferably 6 or more, and further preferably 9 or more. On the other hand, for the purpose of not significantly reducing the heat resistance and mechanical strength of the resin composition molded product of the present invention. It is preferably 25 or less, more preferably 20 or less.

Specific examples of the organic ligands will be given below. In these examples, the functional groups in (b) to (e) correspond to the functional group X in the general formula (3). (A) Metal alkoxide group-containing organic ligand: 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-carboxy Alkoxysilanes such as ethyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriisopropyloxytitanium, n-butyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane. Alkoxy titanium such as silane.

(B) Sulfur-containing organic ligand: mercaptoethane, 1-mercapto-n-butane, 1-mercapto-n-hexane, mercaptocyclohexane, 1-mercapto-n-octane, 1-mercapto-n Mercaptoalkanes such as decane, polyethylene glycols represented by the following general formula (4) having a mercapto group at one end, and ω-mercapto fatty acid esters of polyethylene glycols represented by the following general formula (5) , 1H, 1H, 2H, 2H-perfluoroalkyl-1-thiols represented by the following general formula (6), thiophenol, 4-methylthiophenol, 4-tert-butylthiophenol, 4-hydroxythiophenol, etc. Thiophenol derivatives, 6-mercapto-n-hexanol and other ω-
Dialkyl sulfides such as mercapto alcohols, dibutyl sulfide, dihexyl sulfide and dioctyl sulfide, dialkyl sulfoxides such as dimethyl sulfoxide, dibutyl sulfoxide and dioctyl sulfoxide, dialkyl disulfides such as dibutyl disulfide, dioctyl disulfide, thiourea and thioacetamide. A compound having a thiocarbonyl group such as thiophene, a sulfur-containing aromatic compound such as thiophene, octyl sulfonic acid, decyl sulfonic acid, dodecyl sulfonic acid, dodecyl benzene sulfonic acid, sulfonic acid such as perfluoroalkyl sulfonic acid, or the following general formula ( [Omega] -mercapto fatty acids, which are raw materials for the esters of 5).

[0091]

Embedded image HS- (CH ₂ CH ₂ O) _n —R ¹ (4)

[0092]

Embedded image HS- (CH ₂ ) _m —COO— (CH ₂ CH ₂ O) _n —R ¹ (5) However, in the general formulas (4) and (5), R ¹ is a hydrogen atom or the number of carbon atoms. It represents a hydrocarbon group of 6 or less, or a benzene ring, and n is a natural number representing the degree of polymerization and is usually 2 ≦ n ≦ 1.
5, preferably 2 ≦ n from the viewpoint of avoiding excessive steric hindrance.
≦ 10, more preferably 2 ≦ n ≦ 5. Further, in the general formula (5), m is a natural number and usually 1 ≦ n ≦ 20,
From the viewpoint of avoiding excessive steric hindrance, the upper limit thereof is preferably 15, more preferably 12, while the lower limit of m is preferably 5 and more preferably 8 from the viewpoint of shielding the surface of the semiconductor ultrafine particles from the external environment. Is.

[0093]

[Image Omitted] HS- (CH ₂ ) ₂ -R ^F (6) However, in the general formula (6), R ^F is a trifluoromethyl group (CF _3- ) or a difluoromethylene group (-CF _2- ).
Represents a perfluoroalkyl group having 1 to 20 carbon atoms.

(C) Phosphorus-containing organic ligand: trialkylphosphines such as triethylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, tridecylphosphine, triethylphosphine oxide, tributylphosphine oxide, trihexylphosphine Oxides, trioctylphosphine oxide (abbreviation TOPO), trialkylphosphine oxides such as tridecylphosphine oxide, aromatic phosphines or aromatic phosphine oxides such as triphenylphosphine and triphenylphosphine oxide,
Phosphonic acids such as n-butylphosphonic acid, n-hexylphosphonic acid, octylphosphonic acid, dodecylphosphonic acid and benzylphosphonic acid, and phosphinic acids such as dioctylphosphinic acid.

(D) Nitrogen-containing organic ligand: a nitrogen-containing aromatic compound such as pyridine or quinoline, triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, triphenylamine,
Tertiary amines such as methyldiphenylamine, diethylphenylamine, tribenzylamine, diethylamine,
Secondary amines such as dibutylamine, dihexylamine, dioctylamine, didecylamine, diphenylamine, dibenzylamine, etc., primary hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, phenylamine, benzylamine, etc. Amines, carboxylic acid esters having an amino group such as nitrilotriacetic acid triethyl ester, and the like.

(E) Carboxylic acid organic ligand: butanoic acid, hexanoic acid, octanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, octadecanoic acid and the like, fatty acids having 4 to 20 carbon atoms, benzoic acid, 4 -A benzoic acid derivative such as octylbenzoic acid and 4-dodecylbenzoic acid. Further, the organic ligand also has an effect of shielding ultrafine particles such as semiconductor crystals from the influence of the atmosphere (especially oxygen gas and water) and light from the outside (hereinafter referred to as “shielding effect”). Have. From the viewpoint of the shielding effect, the organic ligand preferably contains a methylene group chain having 4 or more carbon atoms, and the effect is particularly exhibited when a protic solvent such as water or ethanol is used in combination in the production process. Exerts remarkably. This is because the methylene group chain forms a kind of hydrophobic barrier on the semiconductor crystal surface due to its hydrophobicity, and polar chemical species such as protic solvent molecules approach the surface of the semiconductor crystal to elute the metal element. It is presumed that this is due to a mechanism that prevents adverse effects. By using the organic ligand having a methylene group chain having 4 or more carbon atoms, specifically, the quantum effect of the semiconductor nanocrystal is often stabilized. The carbon number of the methylene group chain is usually 4 to 20, preferably 5 to 16, most preferably about 6 to 12.

Although the specific coordination chemical structure of the above organic ligand on the surface of the semiconductor ultrafine particles has not been sufficiently clarified,
In the present invention, the functional group X in the general formula (3) does not necessarily have to retain the structure as it is. For example, in the case of a mercapto group (SH), a transition metal element M (for example, II-VI) existing at the terminal of a semiconductor crystal or a transition metal crystal is used.
In the case of a phosphine oxide group (P = O), the structure is changed to a structure (for example, an S-M structure) in which a covalent bond is formed with zinc or cadmium in a group compound semiconductor and gallium or indium in a group III-V compound semiconductor. , A structure that forms a covalent bond with the transition metal element M (for example, P—O—
It is also possible to change to a structure of M).

The amount of the organic ligand bound to the semiconductor ultrafine particles is usually 5 to 80% by weight, preferably 10 to 60% by weight as a weight percentage (wt%) with respect to the total of the semiconductor ultrafine particles and the organic ligand. %, More preferably 15-40
wt%. The weight percentage can be estimated by analysis by a combination of various analysis techniques such as nuclear magnetic resonance spectrum (NMR), infrared absorption spectrum (IR), elemental analysis, or thermogravimetric analysis (TG).

[Method for Producing Molded Article Using Thermoplastic Resin Composition] The method for producing the resin composition molded article of the present invention is not limited, but the thermoplastic resin composition having the semiconductor ultrafine particles dispersed therein is used. In this case, a method of pressure-molding while maintaining the temperature under a temperature condition 10 to 80 ° C. higher than the glass transition temperature of the thermoplastic resin composition (hereinafter referred to as “heat-retaining press molding”) is preferable. In such heat insulation press molding, a lump of a thermoplastic resin composition in which semiconductor ultrafine particles as a raw material for a molded body are dispersed (hereinafter referred to as "raw material lump") is first prepared,
This is pressure-molded. The pressure molding pressure is usually 10 to 20.
It is 000 g / cm ² .

Since the above-mentioned raw material mass is shaped by the heat insulation press molding and becomes the target molded body as it is, it is usually preferable that the target molded body does not contain undesired inclusions such as bubbles and foreign matters. The size of such raw mass,
There is no limitation on the shape and the manufacturing method, and for example, a known extrusion molding method such as extruding a molten resin from a die having a slit tip such as a T-die or casting a resin solution, an injection molding method, or a process of casting a resin solution, etc. Can be manufactured by Among such molding methods, a molecular weight suitable for molding, the strength of molecular orientation during molding, removal of residual solvent,
In addition, considering the transferability from the mold to be used and the ease of orientation relaxation during the heat press treatment, injection molding without solvent is more preferable as the molding method of the optical component because the resin used has high fluidity. desirable.

In the above heat insulation press molding, the birefringence value is not limited at the stage of the raw material lump, and when the thermoplastic resin matrix has crystallinity, the opaque state due to such crystallization is contained at the stage of the raw material lump. May be. The remarkable effect of the above heat insulation press molding is that it enables a very small molding residual strain (for example, evaluated by birefringence), which means that the polymer chains of the thermoplastic resin matrix are retained by the heat retention at the above temperature conditions. Is possible and has no excessive viscous fluidity. That is, the optical strain that may be contained in the raw material mass and the opaque state due to the above crystallization are thermally relaxed by the heat retention to be eliminated and become a homogeneous transparent state, and at the same time, the process is shaped. is there. Also, due to such thermal relaxation,
In some cases, the effect of reducing the directional anisotropy of dimensional stability of the obtained resin composition molded article can be obtained.

The lower limit of the above-mentioned heat retention temperature range (temperature difference from the glass transition temperature) depends on the properties of the thermoplastic resin matrix used, but if it is too small, the residual molding strain which remarkably appears in birefringence may increase. Therefore, preferably 20 ° C,
More preferably, it is 30 ° C. On the other hand, the upper limit of the heat retention temperature range depends on the properties of the thermoplastic resin matrix used, but if it is too large, the surface flatness and productivity of the molded article may decrease, so it is preferably 70 ° C., more preferably 60.
℃.

Molded product obtained by the above heat insulation press molding
There are no particular restrictions on the temperature conditions of the cooling process, but heating and cooling
In order to reduce the cycle time of
The temperature condition is 10 to 30 ° C. lower than the glass transition temperature.
Preferably. The lower limit of the above pressure molding pressure is
Too small depending on the nature of the thermoplastic matrix
If so, the surface flatness may deteriorate, so 3 is preferable.
0 g / cm ², And more preferably 50 g / cm²Is. one
The upper limit of the pressure molding pressure is the thermoplastic resin mat to be used.
Depending on the nature of the lix, if it is too large, the birefringence of the molded product will
Since it may increase, it is preferably 15000 g / cm.
², And more preferably 10000 g / cm²Is.

The pressure molding pressure in the above heat insulation press molding is at least the last pressure which is maintained at the above heat insulation temperature.
The time average of minutes (hereinafter referred to as “final pressure”) is 0 to
It is preferably 1000 g / cm ² . If this value is too small, the transfer accuracy from the flat surface may not be sufficient, and if it is too large, relaxation of the polymer chains of the thermoplastic resin matrix will be insufficient even if the heat retention temperature is increased, and birefringence will increase. Not reduced to the target. In view of these points, the lower limit of the final pressure is preferably 10 g / cm ^2, more preferably 20 g / cm ^2, more preferably 40 g / cm ²
On the other hand, the upper limit is preferably 500 g / cm ² ,
More preferably 200 g / cm ² , and even more preferably 10
It is 0 g / cm ² .

In the heat insulation press molding of the present invention,
The heating time and the cooling time are not particularly limited, but it is industrially advantageous to shorten the heating time and the cooling time of the equipment as much as possible without impairing the temperature uniformity. Generally, the heating time at the above-mentioned heat retention temperature is usually several seconds to 1 hour, preferably several seconds to 30 minutes, more preferably 1 to 20.
Minutes.

The heating rate up to the heat retention temperature is usually 5
˜70 ° C./min, preferably about 20 to 50 ° C./min. If this speed is too slow, the cycle time becomes long, which causes a problem in industrialization, and the time of exposure to high temperature becomes long, which may cause a problem of thermal deterioration. On the other hand, if it is too fast, uniform heating tends to be hindered. The cooling rate from the above-mentioned heat retention temperature is usually 5 to 50 ° C /
Min., Preferably 10 to 40.degree. C./min.
If this speed is too slow, the cycle time becomes long, which causes a problem in industrialization, and the time of exposure to high temperature becomes long, which may cause a problem of thermal deterioration. On the other hand, if the speed is too fast, uniform cooling is hindered, and distortion due to cooling locally remains, which may adversely affect dimensional stability and birefringence.

Further, in the above heating and cooling, the accuracy of temperature control of each part is extremely important. Within the effective range of the heating stage (pressurized hot plate) of the press machine, if there is a temperature difference of 10 ° C or more at a certain moment during heating / cooling, the dimensional accuracy of the molded product is impaired and warpage occurs. Or, the birefringence may not be sufficiently reduced. From the above, as a heating press machine suitable for the heat insulation press molding in the present invention, use of a high precision press machine capable of precisely and quickly controlling heating and cooling of the entire heating stage by circulating a heating medium is used. desirable.

In the heat insulation press molding, the surface roughness Ra of the portion constituting the plane of the surface for pressing and transferring the raw material block from above and below is preferably 0.1 μm or less. If this value is too large, for example, when assembled in a liquid crystal display device or the like, problems such as color bleeding occur and the image quality deteriorates. Furthermore, even when considered as a general optical member, irregular reflection on the surface,
A scattering problem occurs and the optical characteristics deteriorate. In order to obtain good image quality and optical characteristics, the Ra value is preferably 0.05 μm or less, more preferably 0.01 μm or less.

The atmosphere for carrying out the above heat insulation press molding is
An atmosphere of an inert gas such as nitrogen or argon or a vacuum is preferable, and in this, a vacuum is particularly preferable. If it is carried out in normal air, the target substrate can be obtained without any problems, but the high temperature and oxygen in the air oxidize the surface of the resin substrate and the surface sandwiching the resin processed body of the transfer medium from above and below. Detachment from the substrate may be difficult. Especially when this flat surface is reused many times, this phenomenon often occurs remarkably. For this reason, the oxygen gas concentration of the atmosphere for performing the above-mentioned heat insulation press molding is 10% by volume or less, preferably 5% by volume or less, more preferably 1% by volume or less, and most preferably 0.1% by volume or less.

Further, in the case of carrying out in vacuum, even if a gap is created between the resin substrate and the flat surface, this portion does not remain as a bubble and is more appropriate as a manufacturing condition. Therefore, the pressure in the system is 10 when performing in vacuum.
0 mmHg or less, preferably 50 mmHg or less, more preferably 20 mmHg or less. In consideration of the above-mentioned points, the hot press machine is equipped with a high-precision surface-finished hot plate and a control system that enables accurate execution of heating / cooling and pressure control and vacuum degree control programs. A high temperature tank vacuum hydraulic press is recommended.

The peeling temperature D (° C.) for peeling from the surface sandwiching the resin composition molded body of the present invention after the above heat insulation press molding is
Glass transition temperature Tg of resin composition (raw material block) which is a raw material
It is desirable that the following mathematical expression (A) be satisfied with respect to (° C.).

[0112]

## EQU00003 ## Tg> D.gtoreq.Tg-120 (A) If the peeling temperature D is too high, it may be deformed during peeling. If it is too low, the molded product may crack or crack due to the difference in linear expansion coefficient between the resin composition and the material of the pressing surface. If the peeling temperature D is within the range of the above mathematical expression (A), the peeling temperature D (° C.) is preferably in consideration of productivity such as quality and yield.

[0113]

## EQU4 ## Tg-20> D ≧ Tg-100 More preferably,

[0114]

## EQU5 ## Tg-40> D ≧ Tg-90 Most preferably,

[0115]

## EQU6 ## It is desirable that Tg-40> D ≧ Tg-60. These steps may be carried out by a batch process or may be a continuous process using, for example, a stainless belt or a turntable. The resin composition molded body of the present invention thus peeled off has the above Tg.
Annealing in a temperature range lower than 10 to 50 ° C. is preferable from the viewpoint of reducing the molding residual strain that remarkably appears in birefringence.

[Production Method of Molded Article Using Crosslinked Resin Composition] There is no limitation on the production method when the crosslinked resin composition is used in the resin composition molded article of the present invention.
It can be suitably produced by a method of curing the polymerizable liquid mixture with heat or active energy rays. This method will be described below. The curing proceeds by the polymerization reaction of the polymerizable monomer that is an essential component of the polymerizable liquid mixture. There is no limitation on the form of this polymerization reaction, and known polymerization forms such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, polycondensation, and ring-opening polymerization can be used. Among these examples of the polymerization method, radical polymerization, polycondensation and ring-opening polymerization are preferable from the viewpoint that a wide range of polymerization conditions such as strict dehydration and degassing are not always insoluble. Radical polymerization is more preferable. preferable. on the other hand,
In order to improve various properties as an optical member, such as light transmittance, dimensional stability and low birefringence, any polymerization method by irradiation with active energy rays is preferable, and the reason is not clear, but the polymerization reaction It is presumed that the initiation is due to the homogeneity of the product as it proceeds homogeneously in the polymerization system in a short time. Therefore, the most preferable polymerization method is radical polymerization by irradiation with active energy rays.

The above-mentioned active energy ray means an electromagnetic wave (gamma ray, X-ray, ultraviolet ray, visible ray, Infrared rays) or particle rays (electron rays, α rays, neutron rays, various atomic rays, etc.). The active energy rays preferably used in the present invention are the above-mentioned electromagnetic waves, and more preferably ultraviolet rays and visible rays, and most preferably ultraviolet rays, because energy and a general-purpose light source can be used.

Therefore, a more preferable polymerization mode is a method in which a photoradical generator (see the above example) which generates radicals by ultraviolet rays is used as a polymerization initiator and ultraviolet rays are used as active energy rays. At this time, if necessary, a sensitizer may be used in combination. The addition amount of the photo-radical polymerization initiator is usually 0.0 with respect to 100 parts by weight of the total of the polymerizable monomers.
It is 1 to 1 part by weight, preferably 0.02 to 0.3 part by weight. If the amount added is too large, not only the polymerization will rapidly proceed to cause an increase in birefringence but also the hue may deteriorate. If it is too small, the composition may not be sufficiently cured. The wavelength of the ultraviolet rays is usually 2
The range is from 00 to 400 nm, and this wavelength range is preferably from 300 to 400 nm. On the other hand, the intensity of the ultraviolet rays is usually in the energy range of 0.1 to 200 J / cm ² , and the irradiation time is usually 1 second to 3 hours, preferably 10 seconds to 1 hour from the viewpoint of reaction promotion and productivity. And When the irradiation energy of such active energy rays or the irradiation time is extremely short, heat resistance, dimensional stability or mechanical properties of the obtained resin composition molded article may not be sufficiently expressed due to incomplete polymerization, and conversely When it is extremely excessive, deterioration such as yellowing may occur, which is represented by deterioration of hue due to light. Irradiation with the active energy ray may be performed in one step or in a plurality of steps. As the source of the radiation, a diffusion ray source in which the active energy ray spreads in all directions is usually used, and it is usually shaped in a mold. Irradiation is performed with the polymerizable liquid mixture and the light source fixed and stationary. It is also possible to use the polymerizable liquid mixture as a coating liquid film on an appropriate substrate (for example, resin, metal, semiconductor, glass, paper, etc.), and then irradiate active energy rays to cure the coating liquid film. is there.

When cationic polymerization or anionic polymerization is carried out as a polymerization method, a photoacid-base generator is usually used in combination. [Applications] The resin composition molded article of the present invention can be suitably used for various display devices such as displays, liquid crystal display devices (for example, liquid crystal display panels), or various optical members.

The resin composition molded product of the present invention has excellent optical properties (transparency, dimensional stability, isotropic optical or dimensional stability, low optical distortion, and ultraviolet absorption of dispersed semiconductor nanocrystals. Optical member (so-called passive) that particularly transmits light due to its resistance to ultraviolet light.
It is preferably used as an optical member). For example, it is used for the above-mentioned passive optical member in an optical functional device having a mechanism for transmitting a light ray containing a wavelength component of 350 to 650 nm including the visible region. As such an optical function device,
Various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide,
Optical amplifiers, etc.), cameras, photographing devices such as videos, and the like.

Examples of the passive optical member in such an optical functional device include a lens, a prism, a panel (plate-shaped molded body), a film, an optical waveguide (film-shaped or fiber-shaped), an optical disk and the like. In such a passive optical member, an optional coating layer as necessary, for example, a protective layer that prevents mechanical damage to the coated surface due to friction or abrasion, a light ray having an undesirable wavelength that causes deterioration of semiconductor crystal particles, a base material, or the like. A light absorbing layer that absorbs, a transmission blocking layer that suppresses or prevents the transmission of reactive low molecules such as water and oxygen gas, an antiglare layer, an antireflection layer, a low refractive index layer, and the like, and a base material and a coated surface. An arbitrary additional functional layer such as an undercoat layer or an electrode layer for improving adhesiveness may be provided to form a multilayer structure. Specific examples of such an arbitrary coating layer include a transparent conductive film and a gas barrier film formed of an inorganic oxide coating layer, a gas barrier film and a hard coat formed of an organic coating layer, and the coating method thereof is a vacuum deposition method, A known coating method such as a CVD method, a sputtering method, a dip coating method or a spin coating method can be used.

Specific examples of the optical member of the present invention will be illustrated in more detail. Lenses for glasses, various lenses such as microlenses for optical connectors, condenser lenses for light emitting diodes, optical switches, optical fibers, optical branching in optical circuits, Optical communication components such as junction circuits, optical multiplex / branch circuits, photochromic devices, liquid crystal substrates, touch panels, light guide plates, retardation plates, various display members, optical disc substrates and optical disc films, etc.
Storage and recording applications including coatings, functional films, antireflection films, optical multilayer films (selective reflection films, selective transmission films, etc.), super-resolution films, ultraviolet absorption films, reflection control films,
Examples include various optical films and coating applications such as optical waveguides and identification function printing surfaces.

[0123]

EXAMPLES The contents and effects of the present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Further, various identifications and analyzes in the synthesis examples and various moldings and evaluations in the examples and comparative examples were performed by the following methods. Unless otherwise specified, the raw material reagents used were those supplied by Aldrich without purification. However, a commercially available solvent was used as a purified solvent by the following purification operation.

[0124] Purification Toluene concentrated sulfuric acid, water, saturated aqueous sodium bicarbonate solution, after further washing in the order of water, dried and then filtered through filter paper over anhydrous magnesium sulfate, large addition of diphosphorus pentoxide (P ₂ O ₅₎ Distilled at atmospheric pressure. Purified methanol: dried with calcium sulfate and calcium hydride, further added with sodium hydride, and directly distilled from this at atmospheric pressure, or anhydrous (“Anhydrous”) grade supplied by Aldrich was used. .

[Method of analysis, molding and evaluation] (1) Nuclear magnetic resonance (NMR) spectrum: manufactured by JEOL Ltd.
JNM-EX270 type FT-NMR (¹H: 270 MH
z,¹³C: 67.8 MHz). Unless specified otherwise
Using deuterated chloroform as a solvent,
Lusilane was measured at 23 ° C. as a 0 ppm control. (2) Infrared absorption (IR) spectrum: manufactured by JASCO Corporation
FT / IR-8000 type FT-IR. Measured at 23 ° C
It was (3) X-ray diffraction (XRD) spectrum: manufactured by Rigaku Corporation
RINT 1500 (X-ray source: copper Kα ray, wavelength 1.541
8Å). It was measured at 23 ° C. (4) Transmission electron microscope (TEM) observation: Hitachi
H-9000UHR transmission electron microscope manufactured by Co., Ltd.
High-speed voltage of 300 kV, vacuum degree during observation of about 7.6 × 10 ^-9T
orr). (5) Photo-excited luminescence (PL) spectrum: Hitachi
Scan with a F-2500 spectrofluorimeter made by Co., Ltd.
Speed 60nm / min, excitation side slit 5nm, fluorescence
Room with a side slit of 5 nm and a photomultiplier voltage of 400 V
The temperature was measured. (6) Absorption spectrum and light transmittance: Hewlett-Packard
Room at Card Company HP8453 type UV / Visible absorptiometer
The temperature was measured. For measuring the light transmittance of a resin composition molded article
Measured at 10 different locations using a 1 mm thick test piece
Then, the arithmetic mean value was used for the following evaluation. (7) Pyrolysis residue rate: Part of the resin composition molding
And perform thermogravimetric analysis (TG) by Seiko Instruments
200 mL / min using TG-DTA320 manufactured by Co., Ltd.
The temperature rising rate is 10 on the aluminum plate under the nitrogen stream.
℃ / min, keep 140 ℃ for 30 minutes, then set maximum temperature 59
0 ° C (Actual temperature just below the sample is about 602 to 603 ° C)
Temperature) for 120 minutes. Thus measured
The percentage of residual residue weight before TG measurement is
This is referred to as the "thermal decomposition residue rate". (8) Insulation press forming: at a predetermined temperature under a nitrogen gas atmosphere
In a heatable oven, the surface roughness Ra is 0.0
A raw material mass of 1 m is placed between two stainless steel plates of 04 μm.
With a spacer with a thickness of m
A sheet having a size of 1 mm was formed. (9) Injection molding: Japan Steel Works JS28A injection molding machine is used.
The mold temperature is the glass transition of the thermoplastic resin composition used.
Set a temperature 30 ° C lower than the transfer point and set the thickness of the sheet to 1 mm.
Molded. (10) Glass transition temperature: Raised by DuPont DSC
The measurement was performed at a temperature of 10 ° C./min. (11) Birefringence: Using a resin composition molded body having a thickness of 1 mm,
Automatic birefringence measuring device (Oak Seisakusho, ADR-150
N) was used to measure at 25 ° C. The measurement is any different 1
The measurement was performed at 0 points and the arithmetic mean value was used for the following evaluation. (12) Hot water test: For a resin composition molded body having a thickness of 1 mm
And soak in distilled water kept at 40 ° C for 1 hour, then
Operation to stand for 1 week in an air atmosphere at 3 ° C and 50% relative humidity
The work was performed and the dimensional change rate was measured. However, the size here
As described above, the rate of change of the law is 2 which is orthogonal to the plane of the molded body.
Establishing straight lines and then measuring the length on each straight line
Define the desired line segment (marked with commercially available black magic ink
The length of each line segment before and after the hot water test
Change of length and the corresponding line of each length change before hot water test
Calculate each percentage for the length of the minute and calculate the arithmetic mean of the percentages.
Is the amount defined by. This is referred to below as "hot water dimensional change.
Rate ”.

[Synthesis Example of Core-Shell Type Semiconductor Ultrafine Particles] Synthesis Example 1: Synthesis of CdS Core Ultrafine Particles Having Silicon Oxide Shell Chang et al .; Am. Chem. So
c. , 116, 6739-6744 (1994) with some modifications. Polyoxyethylene nonylphenyl ether (average degree of polymerization: 5) is dispersed in cyclohexane to prepare a transparent reverse micelle solution, which is exactly divided into two equal parts. An aqueous solution of ammonium sulfide and an aqueous solution of cadmium nitrate (both having a concentration of 0.15 mol / L) were prepared and added in equal amounts to the above-mentioned bisected reverse micelle solution.
Obtain the reverse micellar solution of the seed. After they are fully equilibrated, they are mixed and left at room temperature overnight. An aqueous ammonium hydroxide solution (concentration: 9.00 mol / L, 75 equivalents to cadmium) and tetraethoxysilane (200 equivalents to cadmium) are added thereto, and the mixture is stirred and reacted for about 18 hours. The produced particles in the reaction solution are precipitated by centrifugation and washed with cyclohexane and then with methanol to obtain the desired CdS core ultrafine particles having a silicon oxide shell. The product is not dried and stored in a wet cake for use in the next step.

Synthesis Example 2: Cd having a silicon oxide shell
Bonding of Organic Ligand to S-Core Ultrafine Particles The CdS core ultrafine particles having the silicon oxide shell obtained in Synthesis Example 1 were dispersed in tetrahydrofuran, and octyltrimethoxysilane and 3-aminopropyltriethoxysilane were mixed with each other while stirring. : 1 molar ratio and heat to reflux for about 18 hours. The residue obtained by concentrating the reaction solution was washed with methanol and dried to give octyltrimethoxysilane and 3
-CdS core ultrafine particles (hereinafter abbreviated as "A-CdS / SiOx") having a silicon oxide shell bonded to the surface with -aminopropyltriethoxysilane as an organic ligand are obtained. The presence of amino groups derived from 3-aminopropyltriethoxysilane is confirmed by IR spectrum.
From TEM observation of A-CdS / SiOx, it is found that the core-shell type ultrafine particles contain CdS nanocrystals having a number average particle diameter of about 6 nm and the total number average particle diameter is 40 to 50 nm.

Synthesis Example 3: Zn having a silicon oxide shell
Synthesis of O-core ultrafine particles Li et al .; Journal of Nano
particle Research, Volume 3, 157-
160 (2001) with some modifications. Zn obtained by hydrolysis of zinc salt (sulfate, nitrate)
O ultrafine particles are dispersed in ethanol, tetraethoxysilane is added, and a small amount of aqueous ammonium hydroxide solution is added.
After the reaction at room temperature for about 5 hours, the produced particles in the reaction solution are precipitated by centrifugation and washed with ethanol.

[Examples] Example 1: Production and evaluation of amorphous polyolefin resin composition and its molded product A-CdS / SiOx 5 parts by weight and JS obtained in Synthesis Example 2
Arton F5023 (lot number: 912260-000), which is an amorphous polyolefin resin supplied from R Company.
02) 95 parts by weight is dissolved in 1,4-dioxane, heated under reflux for 1 day or more, and then concentrated under reduced pressure to obtain a yellow transparent resin composition. The saturated water absorption of this resin composition measured by the ASTM D570 standard at 60 ° C. and relative humidity of 90% is about 0.3% by weight. This resin composition was molded into a flat plate having a thickness of 1 mm by the above heat insulation press molding, and the light transmittance per 1 mm of the optical path length at the wavelength of sodium D rays was measured to be a value of 70 to 80%. The thermal decomposition residue rate of this resin composition is about 2.5% by weight. In the TEM observation of this resin composition, the particle size is 60
Ultrafine particles of nm or more are 1% by volume or less with respect to the volume of all ultrafine particles. Using the above flat plate with a thickness of 1 mm, wavelength 3
When the light transmittance per 1 mm of the optical path length at 50 nm was measured, it was 10 due to the absorption effect of the contained CdS crystal.
The value is less than or equal to%. When the glass transition temperature of this resin composition is measured, the measured value of 165-175 degreeC is obtained. When the average of the birefringence per 1 mm of the optical path length of the flat plate with a thickness of 1 mm is obtained, the value is less than 10 nm. Above thickness 1m
The dimensional change rate of hot water of the flat plate of m is about 0.01%.

Example 2 Production and Evaluation of Crosslinked Acrylic Resin Composition Molded Article 5 parts by weight of A-CdS / SiOx obtained in Synthesis Example 2 and bis (hydroxymethyl) tricyclo [5.2.1.
[0 ^2,6 ] decane dimethacrylate (95 parts) is mixed, heated and stirred at 80 ° C. under a nitrogen atmosphere, and azobisisobutyronitrile (commonly known as AI) is used as a heat radical generator before solidification.
BN) 0.5 part by weight of dissolved methylene chloride was added, and the mixture was poured into a gap between two stainless steel plates used in the above heat insulation press forming, which had a thickness of 1 mm as a spacer, and was dried at about 80 ° C. under a dry nitrogen atmosphere. The radical polymerization proceeds by heating. Further, by heating at 120 ° C. for 60 minutes, a yellow transparent sheet-shaped resin composition molded product having a thickness of 1 mm is obtained. ASTM D5 of this resin composition molded body
According to the 70 standard, the saturated water absorption measured at 60 ° C. and 90% relative humidity is about 0.3% by weight. When the light transmittance of this resin composition molded article at an optical path length of 1 mm at the sodium D-line wavelength is measured, the value is 70 to 80%.
The thermal decomposition residue rate of this resin composition molded body is about 2.5% by weight. In TEM observation of this resin composition molded body, the amount of ultrafine particles having a particle size of 60 nm or more is 1% by volume or less based on the volume of all ultrafine particles. When the light transmittance of this resin composition molded article per 1 mm of optical path length at a wavelength of 350 nm is measured, the value is 10% or less due to the absorption effect of the contained CdS crystal. The glass transition temperature of this resin composition molded body is about 130 ° C.
When the average of the birefringence per 1 mm of the optical path length of this resin composition molded body is obtained, the value is less than 3 nm. The dimensional change rate of hot water of this resin composition molded body is 0.01% or less.

[0131]

Industrial Applicability The resin composition molding of the present invention has a high degree of transparency, excellent light resistance and low water absorption rate because it contains semiconductor ultrafine particles having an oxide shell in a uniformly dispersed state. When the semiconductor ultrafine particles have ultraviolet absorptivity, they retain their properties and are therefore excellent in ultraviolet resistance. In addition, it also has the effect that the optical distortion evaluated by birefringence is small.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 20/20 C08F 20/20 4J100 20/36 20/36 290/06 290/06 299/02 299/02 C08J 5/00 CEY C08J 5/00 CEY C08K 9/02 C08K 9/02 9/04 9/04 // B29L 11:00 B29L 11:00 F term (reference) 4F071 AA01 AA33 AA33X AA86 AB18 AD02 AD06 AF30Y AF31Y AF45 AF54Y AF62Y AH03 BB03 BC12 4F204 AA21 AA24 AA28 AA29 AA31 AA38 AA42 AB16 AB17 AH73 AM28 AM30 AR03 AR06 FA01 FB01 BC01 BC01 BC4 BC1 BC01 BC01 BC1 BC1 BC01 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC1 BC0 CF081 CG001 CH071 CL031 CN011 CN031 DA056 DA116 DD076 DD086 DE116 DF016 DG026 DG066 DH006 DJ006 DK006 DM006 EW016 FB076 FB086 FB096 FB106 FB136 FB146 FB 156 FB236 FD010 GH00 GP02 GS02 4J027 AC01 AC06 AE10 AG33 AG36 AH03 AJ08 BA19 BA24 BA26 BA27 CA12 CA14 CA15 CA16 CA17 CA18 CA34 CB10 CC02 CC04 CC05 CC06 CC08 CD03 CD04 CD05 CD08 4A100P DA62 DA63 JA01 JA32 JA33 JA35 JA36

Claims (23)

[Claims] 1. A number comprising an inner core which is a semiconductor crystal and an outer shell which is an oxide of at least one element selected from aluminum, silicon, zirconium, tin and antimony provided on the surface thereof. Containing core-shell type semiconductor ultrafine particles having an average particle size of 1 to 50 nm,
A resin composition having a light transmittance of 70% or more per 1 mm of optical path length at a sodium D-line wavelength, and a saturated water absorption rate of 0.4% by weight or less measured at 60 ° C. and 90% relative humidity according to ASTM D570 standard. object. 2. The resin composition according to claim 1, wherein the semiconductor crystal is a titanium oxide crystal, a zinc oxide crystal, or a cerium oxide crystal. 3. The residue obtained by pyrolyzing for 120 minutes at 600 ° C. in a nitrogen atmosphere has a weight of 1 to 6 before the pyrolysis.
It is 0%, The resin composition of Claim 1 or 2. 4. The resin composition according to claim 1, wherein the proportion of the ultrafine particles having a particle size of 60 nm or more is 10% by volume or less based on the volume of all the ultrafine particles. 5. The resin composition according to claim 1, which has a light transmittance of 30% or less per 1 mm of optical path length at a wavelength of 350 nm. 6. The resin composition according to claim 1, which has a glass transition temperature of 150 ° C. or higher. 7. The resin composition according to claim 1, wherein the core-shell type semiconductor ultrafine particles have an organic ligand bonded thereto. 8. The organic ligand contains a functional group of any one of an amino group, a hydroxyl group, a mercapto group, a carboxyl group, an acryloyl group, a methacryloyl group and an epoxy group in its molecular structure. The resin composition described. 9. The polymer constituting the resin matrix contains a functional group of any one of ester bond, amide bond, carbonate bond, urethane bond, urea bond and carbon-carbon double bond in its molecular structure. The resin composition according to any one of claims 1 to 8. 10. A metal crystal alkoxide containing a functional group of any one of an amino group, a hydroxyl group, a mercapto group, a carboxyl group, an acryloyl group, a methacryloyl group and an epoxy group in a molecular structure, mainly composed of semiconductor crystals and having a number average particle size. The method for producing a resin composition according to claim 1, which comprises an essential step of binding to ultrafine particles having a diameter of 1 to 50 nm. 11. A resin composition molded body, which comprises the resin composition according to claim 1 as a main component and has an average birefringence per 1 mm of optical path length of 10 nm or less. 12. The resin composition molded article according to claim 11, which has a minimum thickness of 0.1 mm or more. 13. The dimensional change rate before and after the hot water test in which the test piece is immersed in hot water of 40 ° C. for 1 hour and then allowed to stand in an air atmosphere of 23 ° C. and 50% relative humidity for 1 week is 0.05% or less. 11. The resin composition molded article according to 11 or 12. 14. The resin composition molded article according to claim 11, wherein the resin composition is a crosslinked resin composition. 15. The resin composition molded article according to claim 14, wherein the crosslinked resin composition is obtained by polymerizing a polymerizable liquid mixture containing a polymerizable monomer. 16. The resin composition molded article according to claim 15, wherein the polymerizable monomer is mainly composed of the following general formulas A and / or B. Component (A): an alicyclic skeleton bis (meth) acrylate represented by the following general formula (1). [Chemical 1] (In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or a methyl group, R ^c and R ^d are each independently an alkylene group having 6 or less carbon atoms, and x is 1 or 2 And y represents 0 or 1, respectively.) Component (B): a bis (meth) acrylate having a sulfur atom represented by the following general formula (2). [Chemical 2] (In the general formula (2), R ^a and R ^b are the same as in the general formula (1), R ^e is 6 carbon atoms, respectively representing. Each Ar represents an alkylene group having 1 to 6 carbon atoms It represents an arylene group or an aralkylene group which is 30, and these hydrogen atoms may be substituted with a halogen atom other than fluorine, each X represents an oxygen atom or a sulfur atom, and when each X is an oxygen atom, At least one of each Y has a sulfur atom or a sulfone group (—SO ₂ —)
When at least one of them is a sulfur atom, each Y is a sulfur atom, a sulfone group, a carbonyl group (—CO—),
And an alkylene group having 1 to 12 carbon atoms, an aralkylene group, an alkylene ether group, an aralkylene ether group,
Represents either an alkylene thioether group or an aralkylene thioether group, and j and p are each independently 1
Is an integer of 5 and k is an integer of 0-10. K is 0
Then X represents a sulfur atom. ) 17. An optical member comprising the resin composition molded body according to claim 11. 18. A raw material lump, which is a thermoplastic resin composition in which ultrafine particles are dispersed, is pressure-molded while being kept warm at a temperature condition 10 to 80 ° C. higher than the glass transition temperature of the thermoplastic resin composition. The method for producing a resin composition molded article according to any one of claims 11 to 13, which is characterized in that. 19. The molding pressure is 10 to 20000 g /
The method for producing a resin composition molded body according to claim 18, which has a size of cm ² . 20. The method for producing a resin composition molded article according to claim 18 or 19, wherein the raw material mass or the resin composition molded article is surrounded by an inert gas atmosphere or vacuum during the pressure molding. 21. The time average of the pressure molding pressure in the last minute or more of the pressure molding is 0 to 1000 (g / cm ² ).
The method for producing a resin composition molded article according to any one of claims 18 to 20, which is in the range of. 22. After pressure molding, the temperature D (° C.) at which the resin composition molded body is peeled from the sandwiched surface is expressed by the following mathematical formula (A) with respect to the glass transition temperature Tg (° C.) of the thermoplastic resin composition. )
The method for producing a resin composition molded article according to any one of claims 18 to 21, wherein the method is within the range. [Formula 1] Tg> D ≧ Tg−120 (A) 23. The polymerizable liquid mixture is cured by heat or active energy rays.
Or the method for producing a resin composition molded article according to item 16.