JP2003155355A - Resin composition molding containing ultrafine particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition molding having high transparency and excellent dimensional stability. SOLUTION: This resin composition molding mainly comprises a resin composition into which ultrafine particle having 0.5-50 nm number-average particle diameter are dispersed and has >=70% average light transmittance based on 1 mm optical path in sodium D line wavelength and <=0.05 dimensional change ratio before and after a heating test in which the molding is left to horizontally stand in an air atmosphere at 150 deg.C, heated for three hours and then left to stand in an air atmosphere at 23 deg.C at 50% relative humidity for one week.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition molded article in which ultrafine particles are uniformly dispersed and which has excellent transparency and dimensional accuracy. Since the resin composition molded article of the present invention has the characteristics of the ultrafine particles, for example, the ultraviolet absorbing ability and the excellent heat resistance, it 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.

On the other hand, optical members such as lenses, prisms, fibers, optical couplers, transparent panels and transparent substrates are often required to have a high degree of dimensional stability. This is a general weakness when comparing organic resin materials with inorganic materials such as glass. It is known that such weak points can be improved by dispersing an inorganic substance in an organic resin material. In this case, it is generally expected that the dimensional stability, which is almost proportional to the volume fraction of the inorganic substance, is good. However, the above-mentioned transparency cannot be achieved by a conventional technique of dispersing an inorganic substance in an organic resin material. In addition, there may be a problem of directional anisotropy of dimensional stability of the molded product due to the shape anisotropy of the inorganic substance. That is, when an inorganic substance having a large aspect ratio, such as glass fiber, is dispersed in an organic resin material, particularly in a thermoplastic molding method such as injection molding or extrusion molding, the glass fiber in the flow direction of the organic resin material Occurs, which causes directional anisotropy of dimensional stability in the molded body.

Further, it is generally recognized that it is necessary to disperse ultrafine particles of an inorganic substance or the like in a resin matrix in a state where secondary aggregation is reduced as much as possible. In order to solve such problems, the following techniques have been proposed as a method of controlling the chemical structure and chemical composition of the surface of ultrafine particles. JP-A-1
In Japanese Patent Laid-Open No. 1-43556, coarse particles are produced by subjecting semiconductor ultrafine particles to surface modification, and further reacting a functional group possessed by the surface modification with a resin (particularly preferably a polymer reaction in a solution). It has been reported that a method of obtaining a resin composition in which semiconductor ultrafine particles are dispersed while suppressing the above-mentioned phenomenon and suppressing aggregation is excellent in transparency. JP-A-5-221640 discloses a technique relating to a resin composition in which trialkoxysilanes are bound to the surface of titanium oxide ultrafine particles and dispersed in a resin matrix. JP-A-11-28
In Japanese Patent No. 6619, the surface of ultrafine oxide particles of titanium oxide, zinc oxide, cerium oxide or the like is made to have a coordinated anionic polymerization catalytic activity to form a polyolefin resin-based polymer film to improve dispersibility in an organic matrix. Techniques for doing so are disclosed. Japanese Unexamined Patent Publication No. 2000-230107 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. JP 2000-95967 A and JP 2
Japanese Patent Publication No. 000-281934 discloses a technique of 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 techniques disclosed in any of these publications have failed to provide a resin composition molded article having both high transparency and excellent dimensional stability.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to contain ultrafine particles in a homogeneously dispersed state and to have excellent transparency and dimensional stability. A resin composition molded body, a method for producing the molded body, and an application of the molded body.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an organic ligand that imparts compatibility or reactivity to a resin matrix having excellent transparency is used. Mold a resin composition using surface-modified ultrafine particles of a specific particle size as a raw material by a thermoplastic molding method in which heat insulation press molding is performed under a specific temperature condition or a cross-linking resin molding method using a specific polymerizable monomer. When it is made into a body, a resin composition molded body having extremely excellent transparency and excellent dimensional stability due to the effect of the organic ligand, that is, the suppression of secondary aggregation of ultrafine particles and the homogeneous dispersion effect. Found that
The present invention has been reached.

That is, the first gist of the present invention is to mainly use a resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm are dispersed, and have an optical path length of 1 mm at a sodium D line wavelength.
The average light transmittance per unit is 70% or more, 150
It is left standing horizontally in an air atmosphere at ℃ for 3 hours and then left in an air atmosphere at 23 ℃ relative humidity 50% for 1 week. The dimensional change rate before and after the heating test is 0.05% or less. And a resin composition molded body.

The second gist of the present invention is that the number average particle size is 0.5.
Mainly composed of a resin composition in which ultrafine particles of ˜50 nm are dispersed, the average light transmittance per 1 mm of optical path length at the sodium D-line wavelength is 70% or more, and immersed in warm water at 40 ° C. for 1 hour, and then A resin composition molded article characterized by having a dimensional change rate of 0.05% or less before and after a hot water test which is allowed to stand for 1 week in an air atmosphere having a relative humidity of 50% at 23 ° C.

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 1
The method for producing a resin composition molded body comprises pressure-molding while keeping the temperature at 0 to 80 ° C. higher.

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

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. [Resin Composition Molded Product] The first resin composition molded product provided by the present invention is mainly composed of a resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm, which will be described later, are dispersed, and sodium D The average light transmittance per 1 mm of the optical path length at the line wavelength is 70% or more, and it is left to stand horizontally in an air atmosphere at 150 ° C for 3 hours and then heated at 23 ° C relative humidity 50%.
The dimensional change rate before and after the heating test of standing for 1 week in the air atmosphere is 0.05% or less.

The rate of dimensional change of the resin composition molded article in the present invention is an arithmetic mean of the rate of dimensional change measured in any given orthogonal direction in a given resin composition molded article. 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.

If the dimensional change rate before and after the heating test is too large, it may hinder precision optical member applications.
Preferably 0.03% or less, more preferably 0.02%
Hereafter, it is most preferably 0.01% or less. The meaning of the above-mentioned heating test is set in consideration of the processing conditions of the heating process repeatedly performed when manufacturing a panel from a molded product of a resin material. That is, the above-mentioned molded body undergoes a plurality of heating steps at the time of panel manufacturing, pixel formation, transparent electrode formation, and alignment film formation, under the conditions of several minutes in the air at around 150 ° C. It is heated for several hours. The conditions of standing at 23 ° C. for 1 week in air are set as a representative example of the storage conditions of the molded body in these heating steps, and set in accordance with the constant temperature and constant humidity conditions described in JIS K-7100. did. The permissible ranges of the temperature, relative humidity and time conditions in the heating test are ± 2 ° C., ± 5% relative humidity and ± 5 minutes, respectively.

In the above heating test, if the amount of dimensional change before and after one test is 0.03%, it means that one side of a 300 mm square sheet shrinks by 90 μm. Currently, the width of one pixel used for color display is about 100 μm, and a shrinkage of 90 μm causes a color shift by the width of one pixel. Ie R
Each pixel of red (red), G (green,) B (blue) is 100μ
In the design in which the stripes are formed in this order with the width of m, the G pixel is arranged at the position of the R pixel and the B pixel is arranged at the position of the G pixel at the end portion of the sheet. Color display is not possible. The degree of such color shift depends on the length of the sheet, but the dimensional change is 0.0
In the case of 2% or less, each color can be displayed at the designed position by placing the design center at the center of the 300 mm square sheet. That is, since the positional deviation from the center of the 300 mm square sheet to the center of each side can be suppressed within 30 μm, 70% or more of the sheet edge can display the original pixel color.

The second resin composition molded body provided by the present invention is mainly composed of a resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm, which will be described later, are dispersed, and has an optical path at a sodium D-line wavelength. The average light transmittance per 1 mm is 7
The dimensional change rate before and after the hot water test, which is 0% or more, is soaked in 40 ° C. warm water for 1 hour, and then allowed to stand for 1 week in an air atmosphere at 23 ° C. and 50% relative humidity is 0.05% or less. It is a feature. The definition of the dimensional change rate in the hot water test and its measuring method are the same as those described in the heating test. 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.
It is 01% or less.

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.

Although the reason why the above two excellent dimensional stability is obtained is not clear, the effect of the polymer chains of the resin matrix being adsorbed on the surface of the filler such as an inorganic substance is that the ultrafine particles having the above-mentioned specific particle size. It is presumed that the extremely large surface area unprecedented due to the use of the above-mentioned compound markedly unexpectedly made it remarkable, and it is presumed that this was because the mobility of the polymer chain was suppressed as a whole of the molded body.

There is no limitation on the method for producing the above resin composition molded article, but a preferable method is to produce a thermoplastic resin composition containing ultrafine particles by melting and shaping with a mold or the like (hereinafter "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 average of the light transmittance per mm of the optical path length at the above-mentioned sodium D-ray wavelength which defines the transparency of the molded resin composition of the present invention (hereinafter referred to as "D-ray transmittance").
If it is too small, the transparency may be insufficient and use as an optical member may be hindered. Therefore, the value of the D-ray transmittance is preferably 80% or more, more preferably 85% or more, and most preferably 89%. % Or more. The term "average" used here means that the measured value of the D-ray transmittance in at least 10 arbitrary points of a given molded body is converted into a value per 1 mm of the optical path length by proportional calculation based on the optical path length in the measurement. It is desirable that the number of measurement points be as large as possible in terms of reliability of the average value.

The minimum thickness of the resin composition molded body of the present invention is usually 0.01 mm, and if it is too small, the mechanical strength of the resin composition molded body may be extremely reduced. Therefore, this minimum thickness is preferred. It is 0.05 mm, more preferably 0.1 mm. In addition, the maximum thickness of the resin composition molded body of the present invention is usually 100 mm, and if this is too large, the light transmittance as a whole of the resin composition molded body may be extremely reduced, so this maximum thickness is preferably It is about 50 mm, more preferably about 30 mm.

The size of the resin composition molded article of the present invention is not particularly limited, but the resin composition of the present invention is characterized by 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 nm and an area of preferably 50 to 50,000 cm ² , 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 ultrafine particles used in the resin composition molded product of the present invention preferably contain an inorganic substance from the viewpoint of dimensional stability. The reason for this is that inorganic substances (for example, inorganic glasses such as amorphous SiO ₂ , semiconductors such as titanium oxides and zinc oxide, metals such as gold and silver, metal salts such as magnesium fluoride) generally have linear expansion coefficients. Is considered to be small, and when it is not water-soluble, it has a feature that its water absorption is small or it is substantially non-water-absorption.

The ultrafine particles used in the resin composition molded product of the present invention are preferably those to which an organic ligand is bonded in order to improve the dispersibility in the resin matrix. 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. If the number average particle size of the ultrafine particles is too small, the characteristics peculiar to the substance forming the ultrafine particles (eg, formation of band structure due to crystallinity of semiconductor)
When the number average particle size is too large, the cohesiveness of the ultrafine particles is extremely increased and the transparency and mechanical strength of the resin composition molded article are extremely decreased or the quantum effect is increased. The characteristic (for example, exciton absorption / emission ability in a semiconductor crystal) may not be remarkable. Therefore, the lower limit of the number average particle diameter is preferably 1 nm, more preferably 2n.
m, more preferably 3 nm, and the upper limit value is preferably 40 nm, more preferably 30 nm, and further preferably 2
It is 0 nm. In terms of transparency of the resin composition molded article 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, based on the volume of all ultrafine particles. More preferably, it is 3% by volume or less.
Numerical values measured from transmission electron microscope (TEM) observation images are used to determine the number average particle diameter and the volume%. 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. Using the particle size determined in this way,
For example, the number average particle diameter is calculated by a known statistical processing method of image data, but it is naturally desirable that the number of ultrafine particle images used in the statistical processing (the number of statistically processed data) is as large as possible. Is at least 50, preferably 80 or more, more preferably 100 or more as the number of the particle images randomly selected from the viewpoint of reproducibility.
The calculation of the volume% is performed by converting the volume of a sphere having the diameter determined by the above as a diameter.

The shape of the ultrafine particles used in the resin composition molded body of the present invention is such that the aspect ratio (the major axis and the minor axis is different from each other in order to reduce the directional anisotropy of the linear expansion coefficient as a whole of the molded body). Ratio) is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3. Most preferred are spheres (ie aspect ratio 1). The residue obtained by thermally decomposing the resin composition molded article of the present invention at 600 ° C. for 120 minutes in a nitrogen atmosphere is usually 3 to 60% by weight before the thermal decomposition. Since such a residue is often derived especially when the above ultrafine particles contain an inorganic substance, the amount of the residue is also an index reflecting the content of the ultrafine particles in the resin composition molded body. If the amount of the above residue is too small, the characteristics of the ultrafine particles may be difficult to develop, so the lower limit value is preferably 5
%, And more preferably 7%. On the other hand, if the amount of the above residue is too large, the transparency and mechanical strength of the resin composition molded article of the present invention may be extremely deteriorated, so the upper limit is preferably 50%, more preferably 40%. . The amount of such a residue may be measured, for example, by heating a given molded body in an electric furnace in a nitrogen atmosphere, and more simply, an arbitrary part of the given molded body is cut and collected. The sample may be used for thermogravimetric analysis (TG) in a nitrogen atmosphere.

The light absorption characteristics of the resin composition molded article of the present invention are not particularly limited depending on the application to which it is applied.
It is preferable that the average of the light transmittances per 1 mm of the optical path length at 50 nm (hereinafter referred to as “350 nm transmittance”) is 50% or less. The term "average" as used herein means that the measured value of the 350 nm transmittance at least 10 arbitrary points of a given molded body is converted into a value per 1 mm of the optical path length by proportional calculation based on the optical path length in the measurement. It is desirable that the number of measurement points be as large as possible in terms of reliability of the average value. 350 listed here
The reason for specifying the specific wavelength of nm is the semiconductor crystal described later (for example, titanium oxide, zinc oxide, cerium oxide, etc.).
When using ultrafine particles containing, since it is possible to effectively absorb the ultraviolet rays of 350 nm or less at which the photodecomposition of the synthetic resin becomes remarkable due to the basic absorption of the semiconductor crystals, as an evaluation index for the absorption capacity of the ultraviolet rays. It lies in being appropriate. If the 350 nm transmittance is too large, the ultraviolet resistance and the ultraviolet shielding property of the resin composition molded product of the present invention may be extremely lowered, so the upper limit thereof is more preferably 30.
%, More preferably 15%, most preferably 5%.

Regarding the heat resistance of the resin composition molding of the present invention, it is preferable that the glass transition temperature (Tg) is 150 ° C. or higher. If the glass transition temperature is too low, the heat resistance of the resin composition molded article of the present invention may be insufficient and the dimensional stability may be deteriorated. Therefore, the value of the glass transition temperature is preferably 160 ° C. or more, more preferably Is 170 ° C
That is all. The measurement of the light transmittance is performed by a differential thermal analysis (DSC) using a sample obtained by cutting an arbitrary portion of a given resin composition molding, and cutting an arbitrary portion of the given resin composition molding. By a dynamic viscoelasticity test (so-called tan δ measurement) of a strip-shaped molded piece obtained by hot pressing a thermoplastic resin composition sampled by processing or cutting, or by heating under a load such as a thermomechanical analysis method (TMA) It is carried out by a known method such as softening temperature measurement for measuring mechanical displacement, and when reliable measurement values give different glass transition temperatures in a plurality of these exemplified measurement methods, the highest measurement value among them is adopted. .

In the resin composition molded product of the present invention, it is preferable that the average of birefringence per 1 mm of the optical path length is 10 nm or less from the viewpoint of low optical distortion. "Average" here
The measured value of birefringence at at least 10 arbitrary points of a given molded body is converted into a value per 1 mm of optical path length by proportional calculation based on the optical path length in the measurement, and It is desirable that the number 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.

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 produced 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.

When the molded product of the resin composition of the present invention contains ultrafine particles containing an inorganic substance, since the inorganic substance is a substance having optical characteristics different from that of the resin matrix which is an organic substance, the organic substance alone is realized as the whole molded body. It may have a characteristic that it has a unique refractive index and an Abbe number that cannot be achieved. 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.

[0033]

In Equation 2] _{n D = -0.005ν D + C (} B) a transparent resin material, birefringence increases as the general optical path length is increased. However, when the above ultrafine particles (particularly, ultrafine particles of an inorganic substance) are dispersed in a thermoplastic resin matrix, there may be a feature that the rate of increase in birefringence becomes smaller than ever, despite the increase in optical path length. . Therefore, in a comparatively thick molded product having a thickness of 0.1 mm or more like the optical member 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 article of the present invention unless the object of the present invention is significantly deviated. As such additives, for example, 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 fibers, carbon black, carbon materials such as graphite, antistatic agents, plasticizers, release agents, defoamers, leveling agents, antisettling agents, surfactants, modifiers such as thixotropy imparting agents, pigments, Colorants such as dyes and hue adjusters are exemplified. These additives may be mixed at the time of producing the resin composition, or may be added at the time of molding. In the resin composition molded product of the present invention, the addition amount of these various additives is appropriately set depending on the use of the molded product, but is usually 10% by weight or less, preferably 5% by weight or less.

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 product 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] When a thermoplastic resin composition containing ultrafine particles is used in the production of the resin composition molded article of the present invention, the type of the thermoplastic resin forming the main body of the resin matrix is selected. Is not limited as long as the above-mentioned transparency condition is satisfied, and may contain a crosslinked polymer component as long as it retains thermoplasticity (a property that it is softened by heating and can be shaped). Preferred as such a thermoplastic resin is ASTM D-1003 (3 m
The light transmittance according to the standard (m thickness) is 70% or more, preferably 80% or more, and more preferably 85% or more.

Various additives may be used in combination with the above-mentioned thermoplastic resin composition unless the object of the present invention is significantly deviated. Examples of such additives are the same as those for the additives to the resin composition molded article of the present invention, and the addition amount thereof is appropriately set depending on the use of the molded article, but usually 10
It is not more than 5% by weight, preferably not more than 5% by weight. The above-mentioned thermoplastic resins are exemplified below, but the thermoplastic resins may be used by mixing an arbitrary number of different kinds as long as the light transmittance is satisfied.

Styrenic resin: A homopolymer of a styrene derivative, and a copolymer resin of a styrene derivative as a main component and a vinyl compound copolymerizable therewith. Styrene derivatives include styrene, α-methylstyrene,
Aromatic vinyl compounds such as p-chlorostyrene, p-methylstyrene and vinylnaphthalene can be mentioned. A rubber component may be allowed to coexist when the aromatic vinyl compound is polymerized. The method for producing the styrene-based resin is not particularly limited, and the styrene resin can be produced by radical polymerization by any conventionally known polymerization method such as bulk polymerization, suspension polymerization, bulk-suspension polymerization, or emulsion polymerization.
Examples of typical styrene resins include polystyrene (PS resin), poly (α-methylstyrene), styrene-acrylonitrile copolymer (SAN resin), styrene-methyl methacrylate copolymer and the like, and these may be used alone. Multiple types may be used in combination. 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 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 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 heated and melted,
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 through 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, preferably used is a repeating unit of a polymer structure such as styrene resin, acrylic resin, aromatic polycarbonate resin and amorphous polyolefin resin 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.

[Polymerizable Liquid Mixture and Polymerizable Monomer] When a crosslinked resin composition is used in the resin composition molding of the present invention, the type of the crosslinked resin forming the main body of the resin matrix is the above-mentioned transparency. There is no limitation as long as the condition of 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 the polymerizable liquid mixture may have a polymerizable property as long as it does not significantly impair the polymerizable property of the polymerizable monomer. You may contain the liquid (solvent) which does not have. Also. Usually, it is preferable to add a polymerization initiator. As such a polymerization initiator,
A photoradical generator that is a compound that has a property of generating a radical by light and a thermal radical generator that is a compound that has a property of generating a radical by heat are common, and known compounds 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, Examples thereof include 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, which 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 part by weight, and if the addition amount is too large, not only the polymerization reaction may proceed rapidly and increase in birefringence but also the hue may be deteriorated.
If it is too small, it may not be able to be sufficiently cured.

As the polymerizable monomer having two or more polymerizable functional groups in the molecule, a crosslinked resin composition having excellent transparency and low birefringence is provided, and thus a (meth) difunctional or more polyfunctional monomer is used. 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.

Among the above-exemplified (meth) acrylates, it is particularly preferable in terms of achieving a good balance between the transparency and the low birefringence of the resulting polymer. Is in use. Component A is bis (meth) having an alicyclic skeleton represented by the following general formula (1).
It is an acrylate.

[0050]

[Chemical 3]

General formula (1) In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or a methyl group, and R ^c and R ^d are each independently an alkylene having 6 or less carbon atoms. A group, x represents 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).

[0053]

[Chemical 4]

General formula (2) 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 has 6 to 30 carbon atoms.
Represents an arylene group or an aralkylene group, 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 the Xs are oxygen atoms, at least one of the Ys is 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.

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 is usually 0.1 to 100 mol% with respect to the total amount of the polymerizable monomers contained in the polymerizable liquid mixture.
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.

[Ultrafine Particles] There are no particular restrictions on the species of the ultrafine particles used in the present invention, and transition metals (eg, gold, platinum, silver, palladium, rhodium, zinc, copper, nickel, iron, etc.) can be used. Transition metal alone or alloys of these transition metals), semiconductors, inorganic ultrafine particles such as salts of metals, ultrafine particles of organic compounds such as pigment crystals and resin fine particles, fullerenes such as C ₆₀ and carbon nanotubes Ultrafine carbon material particles and the like can be used.
The effect that the semiconductor ultrafine particles among these give the resin composition molded article of the present invention functional characteristics such as light absorption characteristics such as ultraviolet absorption ability, light emission, antistatic properties, light absorption saturation characteristics, and high refractive index Is preferred because it has

When the particle size distribution of the ultrafine particles is smaller, the homogeneity of dispersibility is improved, and when the ultrafine particles containing a semiconductor crystal have an exciton absorption / emission band, the wavelength width thereof is reduced, which is preferable. There is. Therefore, the standard deviation of the particle size distribution is usually controlled to 20% or less, preferably 15% or less, and more preferably 10% or less.
However, applications that utilize the high refractive index and basic absorption of ultrafine particles (UV absorption applications, reflection control films, optical waveguides, etc.)
In such cases, the particle size distribution may not be a problem.

The ultrafine particles used in the present invention may have a heterogeneous structure such as a mixed crystal or a core-shell structure (a two-layer structure of a core as an inner core and a shell as an outer shell containing the same) described later. Good. In particular, when the core substance has an unfavorable action such as the photocatalytic activity of the semiconductor crystal that is the core promoting the decomposition of the resin matrix, the core-shell structure is provided with a shell of another substance that does not have such an unfavorable action. There may be an excellent effect of improving. Therefore, it is desirable that a chemically relatively inert substance constitutes the shell. Specifically, non-transition metal oxides such as silica (silicon oxide) and alumina (aluminum oxide), nitrides such as boron nitride, etc. Examples of preferable shell substances include simple carbon such as graphitic carbon and amorphous carbon, or noble metals (silver, gold, platinum, copper, etc.).

The above ultrafine particles may be composed of a plurality of types, or even the ultrafine particles of the same kind of substance may have their particle size distribution, such as a two-peak distribution, arbitrarily changed as necessary. [Semiconductor Crystal] A semiconductor crystal has characteristics such as electromagnetic wave absorption (hereinafter simply referred to as “absorption” unless otherwise specified) and a high refractive index according to the energy difference (band gap) between the valence band and the conduction band. Therefore, it is particularly useful as a constituent substance 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 a semiconductor nanocrystal, the fundamental absorption of the semiconductor crystal (Fundamental)
Excitons appearing in a slightly lower energy range than the absorption edge on the long wavelength side of absorption.
The (n, exciton) absorption band has a feature that not only the energy width is extremely small, but also the exciton level is isolated from the conduction band level and the interaction probability with the adjacent energy level is relatively small.

By using ultrafine particles containing a semiconductor crystal having a light emitting property, the resin composition molded article of the present invention is 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 is not particularly limited.
However, a concrete composition example is given as an element symbol or composition formula.
If you show, C, Si, Ge, Sn, etc. periodic table group 14 element
Elemental element, P (black phosphorus), etc.
Body, simple substance of Group 16 element of the periodic table such as Se and Te, SiC
SnO, a compound consisting of a plurality of periodic table group 14 elements such as
₂, Sn (II) Sn (IV) S₃, SnS₂, SnS, SnS
Periodic table of e, SnTe, PbS, PbSe, PbTe, etc.
A compound of a Group 14 element and a Group 16 element of the periodic table, BN,
BP, BAs, AlN, AlP, AlAs, AlSb,
GaN, GaP, GaAs, GaSb, InN, In
Periodic Group 13 elements such as P, InAs, InSb, etc.
Table Compounds with Group 15 elements (or III-V compounds
Semiconductor), Al₂S₃, Al₂Se₃, Ga₂S₃, Ga₂S
e₃, Ga₂Te₃, In₂O₃, In₂S₃, In₂Se₃,
In₂Te₃Periodic table group 13 element and periodic table group 16 element
Periodic table of compounds such as TlCl, TlBr, and TlI
A compound of a Group 13 element and a Group 17 element of the periodic table, Zn
O, ZnS, ZnSe, ZnTe, CdO, CdS, C
Circulation of dSe, CdTe, HgS, HgSe, HgTe, etc.
Compounds of group 12 elements in the periodic table and group 16 elements in the periodic table
II-VI group compound semiconductor), As₂S₃, As₂S
e₃, As₂Te₃, Sb₂S₃, Sb₂Se₃, Sb₂T
e₃, Bi₂S₃, Bi₂Se₃, Bi₂Te₃Periodic table number such as
Compound of Group 15 element and Group 16 element of the periodic table, Cu
₂O, 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 of ZnO, α-Fe ₂ O ₃ , rutile type or anatase type titanium dioxide, Ce ₂ O _{3 and the} like have light absorption ability, high refractive index, safety and low cost. 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 molded resin composition of the present invention almost colorless and transparent and exhibiting excellent ultraviolet absorbing ability are 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, Al, Mn, Cu, Zn, Zr, A as a trace amount of doping element (meaning impurities intentionally added) may be added if necessary.
Elements such as g, Cl, Ce, Eu, Tb and Er may be added. For example, by adding Eu to Y ₂ O ₃ and adding Ag, Cu, Tb, Mn or the like to ZnS, a phosphor having the doping 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 according to 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. (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 semiconductor raw material, they 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. [Other method for producing ultrafine particles] For producing the transition metal ultrafine particles, for example, G. Schmid edition; "Clust
ers and Colloids ”, VCH (We
Inheim, 1994) and the like, a known method for producing a metal colloid utilizing a redox reaction can be used. For example, a solution reaction in which a transition metal ion compound such as chloroauric acid, silver nitrate, or silver perchlorate or a salt thereof is brought into contact with a reducing agent such as citric acid or a salt thereof, a borohydride salt, or an alcohol such as ethanol, or It can be synthesized by a reduction reaction utilizing a physical action such as irradiation with ultrasonic waves or light. M. Brust et al .; Chem. Soc. Che
m. Commun. , 801 (1994), for the purpose of surface modification with an organic ligand soluble in an organic solvent when the redox reaction is carried out in an aqueous phase, and extracting ultrafine particles into the organic phase. Alternatively, the reaction may be performed in a two-phase system with an organic solution of such an organic ligand. Alternatively, the aforementioned W.
W. An improved method recently reported in the literature by Weare et al., Namely, a water / toluene two-phase system in which a starting metal compound such as chloroauric acid and a quaternary ammonium salt such as tetraoctylammonium bromide are replaced with nitrogen to replace dissolved air. A chemical species, AuCl (PPh ₃ ), which is produced by reacting with triphenylphosphine (abbreviated as PPh ₃ ) and dissolved therein, is further reduced with sodium borohydride to have an extremely narrow average particle size of about 1.5 nm. Gold nanocrystals with PPh ₃ having a particle size distribution as an organic ligand (theoretical composition is Au ₁₀₁ (PPh ₃ ) ₂₁ Cl
_The method of obtaining ₅ ) is also suitably applicable to the present invention. In addition, Nanoprobes, Inc. Company (Stony
Brook, New York, USA) to Nanogo
Commercially available products such as gold nanocrystals supplied under the trade name ld may be used in the present invention.

The transition metal ultrafine particles obtained by the above-mentioned redox reaction can be subjected to a desired surface modification by an organic ligand exchange reaction with thiols and amines. That is, L. O. B
row et al .; Am. Chem. Soc. , 119
Vol., 12384-12385 (1997), organic ligand exchange by alkanethiols such as 1-octadecanethiol, or L. O. Brown et al .;
J. Am. Chem. Soc. , 121, 882-8
83 (1999), it is possible to exchange organic ligands with aminoalkanes such as 1-pentadecylamine. Particularly, the latter method is performed in an organic solvent such as methylene chloride at room temperature for about 3 days. By doing slowly,
It is a preferable reaction because it can be precisely controlled from an initial particle size of about 1.5 nm to about 5 nm. Therefore, by carrying out such a controlled organic ligand exchange reaction using an organic ligand having a desired functional group, in principle surface modification introducing a desired functional group can be performed with precise particle size control. It is possible to do.

Ultrafine particles of a transition metal salt or crystals of various functional molecules can be produced by a pulverization method, a solution method such as a precipitation method from a solution or a method utilizing a reaction in a supercritical liquid. is there. [Organic Ligand] When the above-mentioned ultrafine particles used in the present invention have organic ligands having compatibility or reactivity with the resin matrix bonded thereto, the dispersibility of the ultrafine particles in the resin matrix is It may be dramatically improved, and the transparency, dimensional stability, or mechanical strength of the resin composition molded product of the present invention may be improved. The effect of such an organic ligand is due to the effect of suppressing the aggregation of ultrafine particles, the effect of improving the compatibility with the resin matrix, or the chemical reaction between the organic ligand and the polymer constituting the resin matrix. It is considered that this is due to a combined effect such as the effect of bond formation. The binding of the organic ligand may improve the electromagnetic properties such as the absorption and emission ability of the 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 ultrafine particles and the polymer constituting the resin matrix, and the second is a polymerization for giving the organic ligand bound to the ultrafine particles and the polymer constituting the resin matrix. Reaction with a polymerizable monomer (may be a copolymerization reaction with the polymerizable monomer) and a subsequent polymerization reaction of the polymerizable monomer, and thirdly, a high reaction ratio of the organic ligand and the resin matrix. The chemical reaction with the molecule and the subsequent binding reaction between the organic ligand and the ultrafine particles, and the fourth is the reaction between the organic ligand and the polymerizable monomer that gives the polymer forming the resin matrix (the polymerization It may be a copolymerization reaction with a monomer), a polymerization reaction of the polymerizable monomer to proceed next, and a bonding reaction of the organic ligand and ultrafine particles to proceed further. For these methods, see also the description in the section "Method for producing molded resin composition".

The effect of the binding of the organic ligands is particularly remarkable when the material of the ultrafine particles is a transition metal (a simple substance or an alloy), a compound semiconductor, an oxide of a non-transition metal, or a zeolite. This is the case for inorganic substances. It is presumed that this is because the interfacial free energy between the resin matrix and the ultrafine particles of the inorganic material is greatly reduced. There is no limitation on the method for binding the organic ligand to the inorganic ultrafine particles and the molecular structure of the organic ligand used for the method, but the molecular structure of the organic ligand is represented by the following general formula (3). It is what is done.

[0078]

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 ultrafine particles, and 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 connecting X and Y.

The functional group X preferably forms a covalent bond or a coordinate bond with the surface of the 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 the surface treatment of oxides such as silica, alumina and titania, or The following functional groups containing elements of Group 15 or 16 of the periodic table, that is, primary amino groups (-
NH ₂ ), secondary amino group (-NHR; where R is a hydrocarbon group having 6 or less carbon atoms such as methyl group, ethyl group, propyl group, butyl group, phenyl group; the same applies hereinafter), tertiary 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), a pyridyl group, A nitrogen-containing functional group such as an amide bond, a phosphine group,
Functional groups containing Group 15 elements in the periodic table, such as phosphorus-containing functional groups such as phosphine oxide groups, phosphoric acid groups, phosphorous acid groups, and phosphine selenide groups, hydroxyl groups, carboxyl groups, β-
Oxygen-containing functional groups such as diketone groups and β-diketonate groups,
Mercapto group (or thiol group), sulfide bond, sulfoxide group, thio acid group (-COSH), dithio acid group (-CSH), sulfonic acid group, xanthogenic acid group, xanthate group, isothiocyanate group, thiocarbamate group, thiophene Periodic table of sulfur-containing functional groups such as rings 1
Examples thereof include functional groups containing a Group 6 element. 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 ultrafine particles, and the acidic groups such as the phosphate group, the carboxyl group, and the sulfonic acid group are the binding force to the oxide semiconductor crystal. It is most preferably used because it is excellent in

When the functional group Y is a functional group having reactivity with the resin matrix, a nucleophilic or electrophilic substitution-reactive functional group such as a hydroxyl group, an amino group, a carboxyl group, an ester group, an amide group, etc. Examples thereof include radically polymerizable groups such as groups, acryloyl groups, methacryloyl groups, maleoyl groups, vinylphenyl groups, vinyl ester groups, vinylamino groups and ethynyl groups.

Of the above examples of the 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, etc. and 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. Regarding the number of carbon atoms of the divalent organic residue R, the mobility required to sufficiently function the compatibility or reactivity of the functional group Y is ensured and the ultrafine particles are protected from unfavorable chemical reactions from the outside. From the viewpoint, the lower limit is preferably 3 or more, more preferably 6 or more, and further preferably 9 or more, while it is preferable for the purpose of not significantly reducing the heat resistance and mechanical strength of the resin composition molded product of the present invention. Is 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 and 3-methacryloyloxypropyltrimethoxysilane, and alkoxytitaniums such as 3-glycidyloxypropyltriisopropyloxytitanium.

(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).

[0085]

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

[0086]

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, its upper limit value is preferably 15, more preferably 12, while the lower limit value of m is preferably 5 and more preferably 8 from the viewpoint of shielding the surface of the ultrafine particles from the external environment. is there.

[0087]

[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: fatty acid having 4 to 20 carbon atoms such as butanoic acid, hexanoic acid, octanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, octadecanoic acid, 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 inorganic ultrafine particles such as semiconductor crystals has not been sufficiently clarified, in the present invention, the functional group X in the above general formula (3) is used. 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 existing at the terminal of a semiconductor crystal or a transition metal crystal
(E.g., zinc or cadmium in II-VI group compound semiconductors, gallium or indium in III-V group compound semiconductors, etc.), a phosphine oxide group (P In the case of = O), a change to a structure in which a covalent bond with the transition metal element M is formed (for example, a structure of POM) is also considered.

The amount of the above organic ligand bound to the ultrafine particles is
As a weight percentage (wt%) with respect to the total of the ultrafine particle main body such as a semiconductor crystal or a transition metal and the organic ligand, it is usually 5
-80 wt%, preferably 10-60 wt%, more preferably 15-40 wt%. Such weight percentage is
It can be estimated by analysis by a combination of various analysis methods 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 in the case of using the thermoplastic resin composition having the ultrafine particles dispersed therein. A method of pressure-molding while keeping the temperature at 10-80 ° 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 (hereinafter referred to as a "raw material lump") of a thermoplastic resin composition in which ultrafine particles serving as a raw material for a molded body are dispersed is first prepared and then pressure-molded. The pressure molding pressure is usually 10 to 20000 g / cm.
^{Is 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 undesirable contents 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 molding residual strain that 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 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 forming 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 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 heat insulation press molding is as follows:
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 a vacuum, even if a gap is created between the resin substrate and the flat surface, this portion does not remain as a bubble and remains 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.).

[0106]

## 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.

[0107]

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

[0108]

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

[0109]

## 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 molding of the present invention has excellent optical properties (transparency, dimensional stability, isotropic optical or dimensional stability, low optical strain, 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 branches 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.

[0117]

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.

[0118] 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
Surface roughness Ra = 0.0 in a heatable oven
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) Resin composition by thermomechanical analysis (TMA)
The linear expansion coefficient of the molded body was measured. Measure any different 6
Percentage to the arithmetic mean of the standard deviation
(Hereinafter abbreviated as “linear expansion anisotropy”, unit%)
Used for value. (13) Surface roughness: Surface roughness measuring instrument (Tokyo Seimitsu Co., Ltd.)
Surface roughness (Ra, single
Position: μm with diamond needle (1 μm R, 90 degree circle)
Pyramid), measurement length 0.5 mm, cut-off value 0.16 m
m, measurement speed 0.06 mm / sec, measured under the condition of straight line correction
did. (14) Heating test: For a resin composition molded body having a thickness of 1 mm
Then, let it stand still in an air atmosphere at 150 ° C for 3 hours.
Heat and then for 1 week in air at 23 ° C and 50% relative humidity
The operation of standing still was performed and the dimensional change rate was measured. However,
As mentioned above, the dimensional change rate is on the plane of the molded body.
2 straight lines that are orthogonal to
Determine any measurable line segment (commercially available black magic ink
Mark and display with) before and after the above heating test
Measure the length change of each line segment in the
Obtain each percentage for the length of the corresponding line segment before the test,
A quantity defined by the arithmetic mean of percentages. This
Hereinafter referred to as "heating dimensional change rate". (15) 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
The rate of change in the method is the same as in the case of the above heating test.
It was justified. This is hereinafter referred to as "warm water dimensional change rate".
Write down.

[Synthesis of Organic Ligands and Semiconductor Nanocrystals
Example] Synthesis example 1: Synthesis example of organic ligand 11-Mercaptoundecanoic acid (1.70 g) and Trier
Tylene glycol monomethyl ether (hereinafter MTEG
50 mL), and concentrated sulfuric acid (manufactured by Kokusan Kagaku Co., Ltd .;
5 drops) in a flask under a dry nitrogen atmosphere and mixed at 60 ° C.
Decompression dehydration at a pressure of 30 mmHg or less while stirring with
It went for about 36 hours in total. Do not stir the reaction solution in a large amount of ice water.
The precipitate obtained by gradually adding the n-hexane / ethyl acetate
(Both manufactured by Junsei Kagaku Co., Ltd.) mixed solvent
The organic phase is washed with saturated aqueous sodium hydrogen carbonate and then with water, and washed with sodium sulfate.
After drying on vacuum, it was filtered, concentrated, and dried under vacuum at room temperature. This
Product of 1735 cm in IR spectrum^-1To
Ester group, 2920cm ^-1And 2845 cm^-1The pea
Each is assigned to a hydrocarbon structure derived from MTEG containing
Gave an absorption band. Further¹H-NMR spectrum
And a reasonable sig that matches the expected structure, as described below.
Since the null and the integral value are given, 1 shown in the following equation (7)
1-Mercaptoundecanoic acid MTEG ester (hereinafter M
TEG-C11SH) was isolated.
It was¹ H-NMR spectrum: 1.25 to 1.67 (multi
Plett, 18 protons, aliphatic chain) 2.33 (triple
Lett, 2 protons, J = 7.6 Hz, raw material carboxylic acid
Methylene group derived from residue) 3.38 (singlet, 3
Proton, methyl group), 3.54 to 3.58 (multiply
Lett, 2 protons, 3.63 to 3.72 (multiply)
Lett, 8 protons, 4.23 (triplet, 2 pt)
Roton, J = 5.0 Hz, MT adjacent to ester bond
Methylene group of EG residue).

[0121]

Embedded image HS (CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₃ CH ₃ (7) Synthesis Example 2: CdSe ultrafine particle air-cooled Liebig reflux tube and Pyrex equipped with a thermocouple for controlling reaction temperature (Registered trademark) trioctylphosphine oxide (hereinafter TOP) in a three-neck glass flask.
O was abbreviated; 4 g), and the mixture was heated to 360 ° C. in a dry argon gas atmosphere while stirring with a magnetic stirrer. Separately, in a glove box under a dry nitrogen atmosphere, selenium (black powder of a simple substance; 0.1 g) was dissolved in tributylphosphine (hereinafter abbreviated as TBP; 6.014 g), and further added to dimethyl cadmium (Strem Chemi).
Cal solution; 97%; 0.216 g) was mixed and dissolved to prepare a raw material solution A, which was sealed in a rubber stopper (a septum supplied from Aldrich) and wrapped in aluminum foil with no gap to prepare a glass bottle protected from light. A portion (2.0 mL) of this raw material solution A was injected all at once into the flask containing TOPO with a syringe, and this time was taken as the reaction start time. 20 minutes after the start of the reaction, when the heat source was removed and the temperature was cooled to about 50 ° C., purified toluene (2 mL) was added by a syringe to dilute, and the purified methanol (10 mL) was further injected to generate an insoluble matter. This insoluble matter is centrifuged (300
(0 rpm), the supernatant was removed by decantation and separated, and vacuum dried at room temperature for about 14 hours to obtain a solid powder. In the XRD spectrum of this solid powder, W
The formation of CdSe nanocrystals was confirmed by observing the diffraction peaks assigned to the 002 plane and the 110 plane of the urtzite type CdSe crystal. The number average particle size of the CdSe nanocrystals was about 4 nm according to TEM observation. The CdSe ultrafine particles thus obtained were irradiated with excitation light having a wavelength of 366 nm from a mercury lamp in a purified toluene solution to give a red emission band (peak wavelength 595 nm, full width at half maximum 43).
nm).

Synthetic Example 3: Core-shell structure CdSe ultrafine particles having a ZnS shell. O. Dabbousi et al .; Phys. Che
m. B, 101, 9463 (1997). This will be described below. TOPO was placed in a three-necked flask made of brown glass in a dry argon gas atmosphere.
(15 g) was added, and the mixture was stirred under reduced pressure at 130 to 150 ° C. for about 2 hours in a molten state. During this period, the operation of restoring the atmospheric pressure with dry argon gas was performed several times in order to replace the remaining volatile components such as air and water. Set temperature to 100
After about 1 hour at 0 ° C., a solution of the solid powder of CdSe ultrafine particles (0.094 g) obtained in Synthesis Example 2 (0.094 g) in trioctylphosphine (1.5 g, hereinafter abbreviated as TOP) was added, and CdS was added.
A clear solution containing e nanocrystals was obtained. This was further stirred under reduced pressure of 100 ° C. for about 80 minutes, then the temperature was set to 180 ° C. and the pressure was restored to atmospheric pressure with dry argon gas. Separately, in a glove box in a dry nitrogen atmosphere, add 1N of diethyl zinc.
Concentration n-hexane solution (1.34 mL; 1.34 mmol) and bis (trimethylsilyl) sulfide (0.23
9 g; 1.34 mmol) was dissolved in TOP (9 mL) to prepare a raw material solution B, which was sealed in a septum and wrapped in aluminum foil with no gap to prepare a glass bottle protected from light. This raw material solution B was added to the above CdS at 180 ° C. with a syringe.
e Dropping into a transparent solution containing ultrafine particles over 20 minutes,
After the temperature was lowered to 0 ° C., stirring was continued for about 1 hour. After standing at room temperature for about 14 hours, the mixture was again heated and stirred at 90 ° C. for 3 hours. The heat source was removed and anhydrous grade (99.8%) n-butanol (8 mL) supplied by Aldrich was added to the reaction solution and cooled to room temperature to obtain a clear red solution. This red solution had no odor of sulfur compounds such as bis (trimethylsilyl) sulfide as a raw material, and instead had a leek-like odor characteristic of selenium. Since the solution of the CdSe ultrafine particles obtained in Synthesis Example 2 did not have such a selenium odor, the selenium atom due to the sulfur atom on the surface of the nanocrystal was promoted with the progress of the intended sulfide formation reaction on the surface of the CdSe nanocrystal. It is presumed that selenium was liberated by some mechanism such as the substitution reaction of 1), and it was considered that CdSe ultrafine particles having a core-shell structure having a ZnS shell were generated as described in the above-mentioned literature. Part of this red solution (8 mL)
Under a dry nitrogen stream at room temperature, purified methanol (16 m
A red insoluble matter was obtained by a precipitation operation in which L) was added dropwise and stirring was continued for 20 minutes. The red insoluble matter was separated by centrifugation and decantation in the same manner as in Synthesis Example 2, and redissolved in purified toluene (14 mL). Using this redissolved toluene solution, a series of purification operations such as precipitation, centrifugation, and decantation were performed again to obtain a solid product. The solid product was shaken with 1 mL of purified methanol, washed, and then separated by decantation. The number average particle diameter of this solid product was about 5 nm according to TEM observation. This solid product gave a transparent red toluene solution, which was irradiated with excitation light having a wavelength of 468 nm to give a red emission band (peak wavelength 597 nm, full width at half maximum 41 nm). This luminescence is similar to that of Synthesis Example 2 at the same solution concentration.
Since the emission intensity was obviously higher than that of the CdSe ultrafine particles obtained in 1., it was converted into a CdSe nanocrystal having a core-shell structure having a ZnS shell, and the contribution of the non-emission process via the surface level etc. was suppressed. It was considered.
In addition, the IR spectrum of this product shows three absorption bands of 294, which are considered to be derived from the alkyl group of TOPO.
Since it was given at ⁰ , 2920, and 2850 cm ^-1 , TO
It was considered that PO was bound to the nanocrystal surface.

Synthesis Example 4: Core-shell structure having MTEG-C11SH as an organic ligand CdSe ultrafine particles Core-shell structure C having ZnS shell obtained in Synthesis Example 3
While the dSe ultrafine particles (0.5 g) were stirred and dispersed in ethanol (Junsei Kagaku Co., Ltd., 8 mL) under a nitrogen atmosphere, the MTEG-C11SH synthesized in Synthesis Example 1 was mixed therein.
(0.4 g) was added and the mixture was heated under reflux for about 20 minutes. By this heating under reflux, the CdSe ultrafine particles having the core-shell structure were dissolved to give a cloudless red ethanol solution. The reaction solution was concentrated under reduced pressure, and n-hexane was added to the residue to obtain about 20.
Sonicate for 2 seconds to disperse, then centrifuge (400
The insoluble matter was separated by decantation at 0 rpm for 6 minutes. The insoluble matter thus separated was redissolved in purified toluene and poured into about 10-fold volume of n-hexane to form a precipitate, which was separated by centrifugation and decantation as described above. The operations of redissolving, precipitating and separating were repeated once again for purification. The solid obtained by vacuum-drying this product at room temperature gave a red solution that was soluble in ethanol or a 50% by weight aqueous ethanol solution and was not cloudy. Such an ethanol solution gave the same emission band as in Synthesis Example 3, and the IR spectrum of the solid product was MTEG.
Since the absorption bands assigned to the -C11SH-derived ester group and the hydrocarbon structure portion were respectively given, and three sharp absorption peaks believed to be derived from the alkyl group of TOPO described in Synthesis Example 3 were not observed, MTEG −
It was considered that C11SH did not substantially change the semiconductor crystal part chemically and a semiconductor nanocrystal in which TOPO was substituted was obtained. The organic content of this solid product was determined to be TG
The quantity determined by measurement was 29% by weight.

Synthesis Example 5: Synthesis of TiO ₂ Ultrafine Particles Having Dialkylsulfosuccinate as Organic Ligand The method described in the above-mentioned literature by Ito et al. Was used as a reference. The procedure will be described below. While stirring an aqueous solution of titanyl chloride having a concentration of 0.1 mol / L, the same volume of an aqueous solution of sodium carbonate having a concentration of 1.5 mol / L was added dropwise at room temperature over 25 minutes. The thus-obtained suspension of white ultrafine particles was purified by an operation in which three steps of centrifugation (4000 rpm), removal of the supernatant by decantation, and washing with water were repeated in this order. However, the purification was carried out until the white turbidity of barium sulfate was not visually observed even if an aqueous barium hydroxide solution was added to the supernatant. The white precipitate thus obtained was stirred and dispersed in dilute hydrochloric acid having a concentration of 0.3 mol / L while stirring 6
By heating at 0 ° C. for about 1 hour, a transparent acidic hydrosol was obtained. This acidic hydrosol was ice-cooled, and one of the alkyl groups was an allyl group and had radical polymerizability, dialkyl sulfosuccinate monosodium salt (manufactured by Sanyo Kasei Co., Ltd., trade name: Eleminol JS-2, lot number 0804831). When an aqueous solution of () was added, a white precipitate was produced, which was separated by centrifugation and decantation. Since this white precipitate was soluble in an organic solvent such as ethyl acetate, it was dispersed in a large amount of water, well stirred and washed with water, then extracted with a mixed solvent of ethyl acetate and n-hexane, dried and concentrated. did. XRD and TE of this concentrated residue
From M, formation of nanocrystals of anatase type TiO ₂ ultrafine particles (number average particle size: about 5 nm) was confirmed. Since this concentrated residue was also soluble in an organic solvent, it is considered that the dialkyl sulfosuccinate residue is TiO ₂ ultrafine particles in which the anatase-type titanium dioxide nanocrystal surface is bonded via a sulfonic acid group. Was given.

Synthesis Example 6: ZnO ultrafine particles L. Spanhel et al .; Am. Chem. So
c. , 113, 2826 (1991). That is, zinc acetate dihydrate (0.8789 g) manufactured by Kanto Chemical Co., Inc. was dissolved in ethanol (40 mL) in a glass flask protected from light, and nitrogen gas bubbling was performed for 30 minutes to replace the dissolved air. , Part of ethanol (24m
L) was distilled to azeotropically remove coexisting water. The liquid temperature was returned to room temperature and ethanol (24 mL) was added thereto, and lithium hydroxide monohydrate (0.235) manufactured by Kishida Chemical Co., Ltd. was added thereto.
2 g) of the powder was added and ultrasonic irradiation was carried out for 10 minutes to obtain a solution containing no non-precipitating solid particles. Since the absorption spectrum of this solution showed an exciton emission band having a maximum at 314 nm, it was confirmed that ZnO ultrafine particles were generated as described in the above literature. Also, this solution is
nm excitation light gave a broad emission band with a maximum at 496 nm. This luminescence was visually white and green.
The number average particle diameter of the ZnO ultrafine particles was about 4 nm according to TEM observation.

[Example] Thickness of 1 mm obtained in the following examples
For the sheet-shaped molded article, the dimensional change rate (unit is%) by the heating test and the hot water test, the light transmittance at the sodium D-ray wavelength and 350 nm wavelength (D-ray transmittance and 350 nm, respectively, unit is%), The glass transition temperature (unit: ° C), the birefringence (unit: nm), the linear expansion anisotropy rate (unit:%), the thermal decomposition residue rate (unit:%) were measured, and the results are shown in Table- Summarized in 1.

Example 1 Preparation of Aromatic Polycarbonate Resin Composition Molded Article Containing Core-Shell CdSe Ultrafine Particles Core-shell CdSe ultrafine particles having MTEG-C11SH obtained in Synthesis Example 4 as an organic ligand (semiconductor nanocrystals) 5 parts by weight of bisphenol A and 95 parts of bisphenol A polycarbonate (hereinafter abbreviated as PC and viscosity average molecular weight of about 25,000) were dissolved in tetrahydrofuran (hereinafter abbreviated as THF) and mixed. The solution was heated in a vat with a Teflon coating to evaporate the THF to yield the core shell structure C above.
A raw material mass of a PC resin composition in which dSe ultrafine particles were dispersed in a PC matrix was obtained. The above heat-insulating press molding was performed using this raw material block under the conditions of a temperature of 200 ° C. and a pressure molding pressure of 40 g / cm ² to obtain a sheet-shaped molded product having a thickness of 1 mm. When the sheet-shaped molded product was analyzed by the TEM observation, the primary particles of the CdSe ultrafine particles having the core-shell structure were dispersed in a substantially non-aggregated state, and no ultrafine particles having a particle size of 60 nm or more were observed. . This sheet-shaped molded product has a core-shell structure CdSe described in Synthesis Examples 3 and 4.
It retained the same luminous ability as the ultrafine particles.

[0128] Example 2: TiO ₂ ultrafine particles having a dialkyl sulphosuccinate obtained in Preparation Synthesis Example 5 of an amorphous polyolefin resin composition molded article containing TiO ₂ ultrafine particles as an organic ligand (semiconductor nano 5 parts by weight of crystals (number average particle diameter of crystal is about 5 nm) and amorphous polyolefin resin (trade name is ARTON) supplied by JSR
95 parts was dissolved in tetrahydrofuran (hereinafter abbreviated as THF) and mixed. The solution was heated in a vat with a Teflon coating to evaporate the THF and remove the Ti
A raw material mass of a resin composition in which O ₂ ultrafine particles were dispersed in an amorphous polyolefin resin matrix was obtained. Using this raw material block, the above heat insulation press molding was performed under the conditions of a temperature of 210 ° C. and a pressure molding pressure of 40 g / cm ² to obtain a sheet-shaped molded body having a thickness of 1 mm. When the sheet-shaped compact was analyzed by the TEM observation, primary particles of the TiO ₂ ultrafine particles were dispersed in a substantially non-aggregated state, and ultrafine particles having a particle size of 60 nm or more were not observed.

Example 3: Preparation of cross-linked acrylic resin composition molding containing core-shell structure CdSe ultrafine particles by thermal radical polymerization Core-shell structure CdSe ultrafine particles having MTEG-C11SH obtained in Synthesis Example 4 as an organic ligand 1 part by weight, bis (hydroxymethyl) tricyclo [5.2.1.0]
^2,6 ] decane-dimethacrylate 99 parts, azobisisobutyronitrile (commonly known as AIB) as a heat radical generator
1 part by weight of N) was dissolved in purified toluene to obtain a turbid-free solution. The polymerizable liquid mixture obtained by distilling off the solvent (toluene) was poured into the gap between the two stainless steel plates used in the above heat insulation press molding and having a thickness of 1 mm as a spacer, and the mixture was dried under a dry nitrogen atmosphere. Radical polymerization proceeds by heating at 80 ° C and further at 120 ° C for 20
By heating for a minute, a transparent sheet-shaped resin composition molded product having a thickness of 1 mm was obtained. When the sheet-shaped resin composition molded body was analyzed by the TEM observation, primary particles of the core-shell structured CdSe ultrafine particles were dispersed in a substantially non-aggregated state, and ultrafine particles having a particle size of 60 nm or more were observed. Was not done. This sheet-shaped resin composition molded body was substantially insoluble in any solvent such as toluene, chloroform, acetone, or tetrahydrofuran, and the core-shell structure Cd described in Synthesis Examples 3 and 4 was used.
It retained the same luminous ability as the Se ultrafine particles.

Example 4 Preparation of Crosslinked Acrylic Resin Composition Molded Article Containing TiO ₂ Ultrafine Particles by Thermal Radical Polymerization TiO ₂ Ultrafine Particles Having Dialkylsulfosuccinate Obtained in Synthesis Example 5 as Organic Ligand 10 parts by weight, bis (hydroxymethyl) tricyclo [5.2.1.
90 parts of 0 ^2,6 ] decane dimethacrylate, azobisisobutyronitrile (commonly known as AIB) as a heat radical generator.
1 part by weight of N) was dissolved in a mixed solvent of ethyl acetate and n-hexane to obtain a turbid solution. The polymerizable liquid mixture obtained by distilling off the solvent (ethyl acetate and n-hexane) was poured into the gap between the two stainless steel plates used in the heat insulation press molding, and a stainless steel plate having a thickness of 1 mm was interposed as a spacer, By heating at about 80 ° C. in a dry nitrogen atmosphere to promote radical polymerization, and further heating at 120 ° C. for 20 minutes, a transparent sheet-shaped resin composition molded product having a thickness of 1 mm was obtained. Analysis of this sheet-like resin composition molded article by the TEM observation, 1 of the TiO ₂ ultrafine particles
Secondary particles are dispersed in a substantially non-aggregated state, and the particle size is 6
No ultrafine particles of 0 nm or more were observed. This sheet-shaped resin composition molded body was substantially insoluble in any solvent such as toluene, chloroform, acetone, or tetrahydrofuran and had an ultraviolet absorbing ability derived from TiO ₂ ultrafine particles.

Example 5: Preparation of crosslinked resin composition containing TiO ₂ ultrafine particles by photoradical polymerization 45 parts by weight of TiO ₂ ultrafine particles having the dialkylsulfosuccinate obtained in Synthesis Example 5 as an organic ligand, Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 45 as polymerizable monomer
Parts and 10 parts by weight of n-butyl methacrylate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide as a photoradical generator (“Lucirin T manufactured by BASF Ltd.
PO ") and 0.5 parts by weight of benzophenone were added and uniformly mixed with stirring, and then defoamed to obtain a polymerizable liquid mixture. This was poured into a mold of optical polishing glass using a 1 mm-thick silicone plate as a spacer, and the temperature was kept at about 80 ° C. in a dry nitrogen atmosphere, and the output was placed 40 cm above and below the surface of the optical polishing glass. 80 W / cm
UV rays were irradiated for 5 minutes between the metal halide lamps. After UV irradiation, the mold was removed, and the mold was heated at 120 ° C. for 20 minutes to obtain a transparent sheet-shaped resin composition molded product having a thickness of 1 mm. When the sheet-shaped resin composition molded body was analyzed by the TEM observation, the primary particles of the TiO ₂ ultrafine particles were dispersed in a substantially non-aggregated state, and the particle size was 60 n.
Ultrafine particles of m or more were not observed. This sheet-shaped resin composition molded body was substantially insoluble in any solvent such as toluene, chloroform, acetone, or tetrahydrofuran and had an ultraviolet absorbing ability derived from TiO ₂ ultrafine particles.

Example 6 Resin Composition Molded Body Obtained by Known Injection Molding Method The raw material block of Example 1 is extruded in a molten state from a thin hole to form a strand (thin molten resin is thinly stretched), and thus obtained strand Was cut with a pelletizer to give pellets. The pellets thus obtained were vacuum dried and then injection-molded to obtain a sheet having a thickness of 1 mm and excellent in transparency.
When the sheet-shaped compact was analyzed by the TEM observation, the primary particles of the TiO ₂ ultrafine particles were dispersed in a substantially non-aggregated state, and no ultrafine particles having a particle size of 60 nm or more were observed. , The birefringence increased.

[Comparative Example] The same evaluation as in the above-described example was carried out. Comparative Example 1: Trial of heat insulation press molding using a conventional semiconductor ultrafine particle resin composition The following experiment was conducted according to the method disclosed in JP-A-11-43556. Cadmium perchlorate hexahydrate (1.0 equivalent), thiophenol (1.5
2 equivalents) and aminothiophenol (1.52 equivalents) in a mixed solution of acetonitrile-methanol (1: 1) (cadmium concentration is about 0.025 mol / L) under stirring in a dry argon atmosphere. Bubbling with dry argon gas containing 5% by volume of hydrogen sulphide. The obtained solution containing semiconductor ultrafine particles was concentrated and mixed with toluene to precipitate the semiconductor ultrafine particles. The precipitate was separated by centrifugation and decantation, dissolved again in methanol, and then mixed with an excess amount of toluene to carry out purification by reprecipitating semiconductor ultrafine particles. This reprecipitation operation was repeated 5 times. Finally, the precipitate was taken out and dried to obtain CdS ultrafine particles considered to have thiophenol and / or aminothiophenol bonded as an organic ligand. The number average particle diameter of the CdS ultrafine particles was about 3 nm. Further, from the IR spectrum by the KBr tablet method, the C—N stretching (1340-1250 cm ⁻¹ ) characteristic of aromatic amines was observed as in the report of the above publication, so that Cd
The presence of amino groups was confirmed on the surface of the S ultrafine particles. This C
After dissolving 1 g of dS ultrafine particles in 20 mL of dimethylformamide, adding 5 g of polyacrylic acid and thoroughly stirring, the amide bond formation reaction between the amino groups on the surface of CdS ultrafine particles and polyacrylic acid taught by the above publication was advanced. Then, it was dried on the above heat-insulating press-forming stainless steel plate to obtain a gel-like yellow transparent resin composition. This resin composition was tried to be heat-insulated press-molded in the same manner as in Example 1. However, even if the heat-insulation press-molding and / or the pressure-molding pressure was increased, the resin composition did not show substantially thermoplasticity, and a desired molded article was obtained. I couldn't. It is presumed that the reason is that the resin composition taught by the above publication is bonded to the semiconductor ultrafine particles and the resin matrix via the organic ligand (that is, substantially chemically crosslinked). Was done.

Comparative Example 2 Trial of Insulation Press Molding Using Conventional Semiconductor Ultrafine Particles In Example 4, a TiO ₂ powder containing a polyoxyethylene-based dispersant supplied from CI Kasei Co., Ltd. as a raw material for ultrafine particles was used. Using an ethanol dispersion of fine particles (having a number average particle size of about 30 nm), the thermal decomposition residue ratio was calculated to be the same as in Example 4, and the mixture was added to the polymerizable monomer, and the same experimental operation was performed. A sheet-shaped resin composition molded body having a thickness of 1 mm was obtained. The resin composition molded body thus obtained was visually opaque, and when this sheet-shaped resin composition molded body was analyzed by the above-mentioned TEM observation, it was found that TiO ₂ ultrafine particles with a particle size of 60 nm or more were among all ultrafine particles. It occupied about 12% by volume. This sheet-shaped resin composition molded article is substantially insoluble in any solvent such as toluene, chloroform, acetone, or tetrahydrofuran,
It had an ultraviolet absorbing ability derived from TiO ₂ ultrafine particles.

Comparative Example 3: When Ultrafine Particles are not Contained In Example 1, only the PC resin is dissolved in THF without mixing the core-shell structure CdSe ultrafine particles, and the same operation is performed below to form a PC resin sheet having a thickness of 1 mm. A molded body was obtained.
Table 2 shows that the heating dimensional change rate and the hot water dimensional change rate are higher than in Example 1, and that the semiconductor nanocrystals are not contained, so the 350 nm transmittance, which represents the ultraviolet ray transmissivity, is increased. I understand.

[0136]

[Table 1]

[0137]

[Table 2]

[0138]

The resin composition molded product of the present invention has a high degree of transparency and excellent dimensional stability because it contains ultrafine particles uniformly dispersed therein. When the ultrafine particles have an ultraviolet absorbing property, they retain their characteristics and thus have excellent ultraviolet resistance. In addition, the optical strain evaluated by the birefringence is small, and the anisotropy of the linear expansion coefficient is also reduced.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/00 C08K 3/00 C08L 101/00 C08L 101/00 F term (reference) 4F071 AA01 AA33 AA33X AA86 AB00 AB18 AD02 AD06 AF30Y AF31Y AF45 AF54Y AF62Y AH19 BB03 BC16 4J002 BB171 BC011 BC031 BC041 BC061 BC071 BC081 BC091 BC111 BG041 BG051 BG061 BG071 DD0686 DA060 DA060 DA060 DA060 DA016 DA076 DA056DA056 DA060 DA060 DE136 DE146 DF016 DG026 DG066 DH006 DJ006 DJ016 DK006 DM006 EW016 FB076 FB086 FB096 FB106 FB136 FB146 FB156 FB236 FD010 GF00 GH00 GP00 GP01 GP02 GS02 4J027 CA01 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 CA14 BA14 CA14 CA14 BA14 CA17 CA14 CA14 CA14 CA14 CA17 BA14 BA17 CA14 CA17 CA14 CA14 BA14 CA17 CA14 CA17 CA14 CA17 CA14 CA14 CC08 CD03 CD04 CD05 CD08 4J100 AL66P BA02P BA08P BA12P BA51P BA58P BB01P BB03P BC07P BC43P CA01 CA23 DA25 DA47 DA62 DA63 JA01 JA32 JA33 JA35 JA36

Claims (24)

[Claims] 1. A resin composition comprising ultrafine particles having a number average particle diameter of 0.5 to 50 nm dispersed therein, and having an average light transmittance of 70% or more per 1 mm of optical path length at a sodium D-line wavelength. , Horizontally standing in an air atmosphere of 150 ° C., heating for 3 hours, and then standing in an air atmosphere of 23 ° C. 50% relative humidity for 1 week. The dimensional change rate before and after the heating test is 0.05% or less. A resin composition molded body characterized by the above. 2. A resin composition mainly comprising ultrafine particles having a number average particle diameter of 0.5 to 50 nm dispersed therein, and having an average light transmittance of 70% or more per 1 mm of optical path length at a sodium D-line wavelength. Resin composition characterized by having a dimensional change rate of 0.05% or less before and after a hot water test in which it is immersed in 40 ° C. warm water for 1 hour and then allowed to stand in an air atmosphere at 23 ° C. and 50% relative humidity for 1 week. Molded article. 3. The resin composition molded article according to claim 1, wherein the ultrafine particles contain an inorganic material. 4. The resin composition molded article according to claim 3, wherein the ultrafine particles contain semiconductor crystals. 5. The semiconductor crystal is any one of a titanium oxide crystal, a zinc oxide crystal and a cerium oxide crystal.
The resin composition molded article according to. 6. The residue obtained by pyrolyzing for 120 minutes at 600 ° C. in a nitrogen atmosphere is 3 times the weight before the pyrolysis.
It is -60%, The resin composition molded object in any one of Claims 1-5. 7. The resin composition molded article according to claim 1, wherein the ratio of the ultrafine particles having a particle diameter of 60 nm or more is 10% by volume or less based on the volume of all the ultrafine particles. 8. The average of light transmittances per 1 mm of optical path length at a wavelength of 350 nm is 50% or less.
7. A resin composition molded body according to any one of 7. 9. The molded resin composition according to claim 1, which has a glass transition temperature of 150 ° C. or higher. 10. The resin composition molded article according to claim 1, wherein the average of birefringence per 1 mm of the optical path length is 10 nm or less. 11. The standard deviation of the directional anisotropy of the linear expansion coefficient is 10% or less of the average of the linear expansion coefficient.
0. The resin composition molded article according to any one of 0. 12. The resin composition molded body according to claim 1, wherein the average of the surface roughness Ra is 0.1 μm or less. 13. The resin composition molded article according to claim 1, wherein the ultrafine particles have an organic ligand bonded thereto. 14. The resin composition molded article according to claim 1, 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 polymerizable monomer has the following general formula A and / or
Alternatively, the resin composition molded article according to claim 15, which is mainly composed of 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. The resin composition molded article according to claim 1, which has at least one functional layer selected from a gas barrier layer, a hard coat layer and a conductive layer on the surface of the molded article. . 18. An optical member comprising the resin composition molded body according to claim 1. 19. A raw material lump, which is a thermoplastic resin composition in which ultrafine particles are dispersed, is pressure-molded under a temperature condition 10 to 80 ° C. higher than the glass transition temperature of the thermoplastic resin composition. A method for producing a resin composition molded body according to any one of claims 1 to 16. 20. Pressure molding pressure is 10 to 20000 g
The method for producing a resin composition molded body according to claim 19, wherein the resin composition molded body is / cm ² . 21. The method for producing a resin composition molded article according to claim 19, wherein the raw material mass or the periphery of the resin composition molded article is an inert gas atmosphere or a vacuum during the pressure molding. 22. 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 19 to 21, which is in the range of. 23. After pressure molding, the temperature D (° C.) at which the resin composition molded article is separated 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 19 to 22, wherein the method is within the range. [Formula 1] Tg> D ≧ Tg−120 (A) 24. 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.