JP2003183414A - Formed body of crosslinked resin composition containing super fine particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a formed body of a crosslinked resin composition having a good transparency together with improved tensile strength and elastic modulus. <P>SOLUTION: The crosslinked resin composition comprises super fine particles with a number average particle diameter of 0.5-50 nm dispersed therein and has a tensile strength of ≥1 MPa and has an average light transmittance of ≥70% per 1 mm of optical path length at the wave length of sodium D line and a minimal thickness of ≥0.1 mm. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crosslinked resin composition molded body in which ultrafine particles are uniformly dispersed and which has excellent transparency and tensile strength. The crosslinked resin composition molded body of the present invention,
Since the ultrafine particles have characteristics such as ultraviolet ray absorbing ability and excellent heat resistance, they are 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. The use of the crosslinked resin matrix has the advantage of exhibiting particularly excellent dimensional stability and solvent resistance due to the effect that many crosslink points significantly restrain the mobility of the polymer chain.

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.

It is generally recognized that it is necessary to disperse ultrafine particles of an inorganic substance or the like in a resin matrix with secondary aggregation reduced as much as possible. In order to solve such a problem, the technology of the following publications has been proposed for controlling the chemical structure and chemical composition of the surface of ultrafine particles. JP-A-11-435
No. 56 discloses that formation of coarse particles is suppressed 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). In addition, a method for obtaining a resin composition having excellent transparency in which semiconductor ultrafine particles are dispersed while suppressing aggregation is reported. 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. Japanese Patent Laid-Open No. 11-286619 discloses a method for forming a polyolefin resin-based polymer film on a surface of ultrafine oxide particles of titanium oxide, zinc oxide, cerium oxide, etc., which has a coordination anionic polymerization catalytic activity to form an organic matrix. Techniques for improving dispersibility 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 2000-2.
Japanese Patent No. 81934 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. JP 2
Japanese Patent Publication No. 001-2417 discloses a technique for improving the dispersibility of titanium oxide ultrafine particles in a resin matrix by using modified polysiloxanes. Although the resin composition technology disclosed in any of these publications can certainly provide a thin film shaped article such as a coating film having a certain degree of transparency, it has a certain minimum thickness of about 0.1 mm or more. It was not possible to obtain a crosslinked resin composition molded product having a high degree of transparency and excellent mechanical strength (particularly tensile strength or elastic modulus).

[0005]

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 uniformly dispersed and to have a minimum thickness of 0.1 mm or more,
It is intended to provide a crosslinked resin composition molded article having excellent transparency and a large tensile strength or elastic modulus, a method for producing the same, and an application of the molded article.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an organic ligand that imparts compatibility or reactivity to a resin matrix having excellent transparency is used. The effect of the organic ligand is obtained by forming a cross-linked resin composition using surface-modified ultrafine particles having a specific particle diameter as a raw material by a cross-linking resin molding method using a specific polymerizable monomer. It was found that a crosslinked resin composition molded body having extremely excellent transparency due to the suppression of secondary aggregation of ultrafine particles and the effect of interfacial adhesion, and having a large tensile strength or elastic modulus was obtained, and reached the present invention. .

That is, the first gist of the present invention consists of a crosslinked resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm are dispersed and which has a tensile strength of 1 MPa or more, and at a sodium D-ray wavelength. The crosslinked resin composition molded body has an average light transmittance of 70% or more per 1 mm of optical path length and a minimum thickness of 0.1 mm or more. The second gist of the present invention resides in a method for producing the above-mentioned crosslinked resin composition molded body, characterized in that the polymerizable liquid mixture is cured by heat or active energy rays.

The third gist of the present invention resides in an optical member comprising the above-mentioned crosslinked resin composition molded body.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
[Crosslinked resin composition] The crosslinked resin composition molded article of the present invention is
It comprises a crosslinked resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm are dispersed and which has a tensile strength of 1 MPa or more. It can be seen that the given molded article is composed of the crosslinked resin composition because the solvent-insoluble component is present when part or all of the molded article is to be dissolved in an arbitrary solvent. The ratio of the solvent-insoluble component to the weight of a part or the whole of the molded product used in the solvent solubility test is usually 1 to 100% by weight, preferably 3 to 100% by weight in terms of dimensional stability and solvent resistance. , And more preferably 5 to 100% by weight.

The above-mentioned tensile strength is measured according to the ASTM-D638 standard using a given molded body itself or a tensile test piece prepared by cutting from the molded body. This is because the crosslinked resin composition does not have sufficient thermoplasticity or solvent solubility, so it is practical to remold a part or all of a given molded body by known melt molding or solution molding. Because it is impossible.

[Crosslinked resin composition molded article] The crosslinked resin composition molded article of the present invention has ultrafine particles having a number average particle diameter of 0.5 to 50 nm dispersed therein and a tensile strength of 1 MPa or more. The average light transmittance is 1% or more and the minimum thickness is 0.1 mm or more at a sodium D-line wavelength. The ultrafine particles will be described in detail later, but when they are combined with an organic ligand described later, they exhibit particularly excellent tensile strength or elastic modulus, and light transmittance. Although the reason for the effect of this organic ligand is not clear, in addition to the effect of suppressing secondary aggregation,
The interfacial adhesion effect in which the polymer chains of the crosslinked resin matrix are adsorbed on the surface of the ultrafine particles such as an inorganic substance becomes extremely unexpectedly remarkable due to the unprecedented very large surface area due to the use of the ultrafine particles having the above-mentioned specific particle size, It is presumed that this is because the mobility of the polymer chains is suppressed as a whole of the molded body, and the mechanical strength is significantly affected.

The determination that a given molded article is composed of a crosslinked resin matrix can be made by confirming the presence of a solvent-insoluble polymer component in a solvent dissolution test. this is,
This is the effect of cross-linking the polymer chains. There is no limitation on the solvent used here, and it is desirable to select a good solvent as much as possible. As a typical solvent with excellent polymer solubility,
Tetrahydrofuran, chloroform, chlorobenzene,
Chloronaphthalene, hexafluoroisopropanol,
Examples are m-cresol and tetrachloroethane. The solvent dissolution test needs to be performed under conditions (temperature, pH, time, etc.) in which the polymer chain cleavage reaction does not substantially proceed. The weight ratio of the solvent-insoluble polymer component in the solvent dissolution test is usually 1 to 100% with respect to the total weight of organic substances determined by thermogravimetric analysis described later, the dimensional stability of the crosslinked resin composition molded article and the solvent resistance. From the viewpoint of sex, it is preferably 5 to 100%, more preferably 10 to 100%.

The method for producing the above-mentioned molded product of the crosslinked resin composition is not limited, but a preferred method is to charge a molding liquid with a polymerizable liquid mixture containing a polymerizable monomer and ultrafine particles described below. Then, a polymerization reaction is performed to form a crosslinked resin composition in the molding die (hereinafter referred to as "crosslinked resin molding method"). If the average light transmittance (hereinafter referred to as "D-ray transmittance") per 1 mm of the optical path length at the sodium D-ray wavelength that defines the transparency of the crosslinked resin composition molded article of the present invention is too small, the transparency is poor. The value of the D-ray transmittance is preferably 80% or more, more preferably 85% or more, and most preferably 89% or more, since it becomes sufficient and may hinder the use as an optical member. The term "average" used here means the measured value of the D-ray transmittance at at least 10 arbitrary points of a given molded article,
The value 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, and it is desirable that the number of measurement points is as large as possible in terms of reliability of the average value.

The minimum thickness of the crosslinked resin composition molded article of the present invention is 0.1 mm, and if this is too small, the mechanical strength of the crosslinked resin composition molded article may be extremely reduced, so this minimum thickness is preferred. Is 0.5 mm, more preferably 1 mm. In addition, the maximum thickness of the crosslinked 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 crosslinked resin composition molded body may be extremely lowered, so this maximum thickness is It is preferably 50 mm, more preferably about 30 mm.

The ultrafine particles used in the crosslinked 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.

If the number average particle diameter of the ultrafine particles is too small, the characteristics peculiar to the substance forming the ultrafine particles (for example, the formation of a band structure due to the crystallinity of the semiconductor) may not be remarkable, and conversely If the number average particle size is too large, the cohesiveness of the ultrafine particles will be extremely increased, and the transparency and mechanical strength of the crosslinked resin composition molded article will be extremely decreased, and the characteristics due to the quantum effect (for example, exciton absorption and emission in semiconductor crystals). Noh) may not be noticeable. Therefore, the lower limit value of the number average particle diameter is preferably 1 nm, more preferably 2 nm, further preferably 3 nm, and the upper limit value is preferably 40 nm, more preferably 30 nm, still more preferably 20 nm.

From the viewpoint of transparency of the crosslinked 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 with respect to the total ultrafine particles.
It is preferably not more than 3% by volume, more preferably not more than 3% by volume. 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. The number average particle diameter is calculated, for example, by a known statistical processing method of image data using the thus determined particle diameter. The number of ultrafine particle images used for the statistical processing (the number of statistically processed data) is as small as possible. It is naturally desirable that the number is large, and in the present invention, the number of the particle images randomly selected from the viewpoint of reproducibility is at least 50, preferably 80 or more, more preferably 100 or more. The calculation of the volume% is performed by converting the volume of a sphere having the diameter determined by the above as a diameter.

The shape of the ultrafine particles used in the crosslinked resin composition molded body of the present invention has an aspect ratio (long axis and short axis) for the purpose of reducing 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 crosslinked resin composition molded article of the present invention at 600 ° C. for 120 minutes in a nitrogen atmosphere is usually 1 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 crosslinked 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 3%, more preferably 5%. On the other hand, if the amount of the above residue is too large, the transparency and mechanical strength of the crosslinked resin composition molded product of the present invention may be extremely deteriorated. Therefore, the upper limit is preferably 50%, more preferably 40%. is there. The amount of such a residue may be measured, for example, by heating a given shaped body in an electric furnace in a nitrogen atmosphere, and more simply, an arbitrary part of the given shaped body is cut and collected. It may be carried out by thermogravimetric analysis (TG) in a nitrogen atmosphere using a commercial product as a sample.

The light absorption characteristics of the crosslinked resin composition molded article of the present invention are not particularly limited depending on the application to which it is applied, but in applications requiring ultraviolet resistance or ultraviolet shielding, per 1 mm optical path length at a wavelength of 350 nm. Average light transmittance (hereinafter referred to as "350 nm transmittance") is 50%
The following is preferable. "Average" here means
The measured value of the above-mentioned 350 nm 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. Is desirable in terms of reliability of the average value. 3 mentioned here
The reason for designating a specific wavelength of 50 nm is that when ultrafine particles containing a semiconductor crystal (for example, titanium oxide, zinc oxide, cerium oxide, etc.) described later are used, the photoabsorption of the synthetic resin is remarkable due to the basic absorption of the semiconductor crystal. 350n
Since it is possible to effectively absorb ultraviolet rays of m or less, it is appropriate as an index for evaluating the absorption ability of the ultraviolet rays. If the 350 nm transmittance is too large, the ultraviolet resistance and the ultraviolet shielding property of the crosslinked resin composition molded product of the present invention may be extremely lowered, so the upper limit is more preferably 30%, further preferably 15%. , Most preferably 5
%.

Regarding the heat resistance of the crosslinked resin composition molded product 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 crosslinked resin composition molded article of the present invention may be insufficient and the dimensional stability may be deteriorated. Therefore, the glass transition temperature is preferably 160 ° C or higher, It is preferably 170 ° C. or higher. The light transmittance is measured by differential thermal analysis (DSC) using a sample obtained by cutting an arbitrary portion of a given crosslinked resin composition molded article as a sample, and an arbitrary portion of a given crosslinked resin composition molded article. Dynamic viscoelasticity test of a strip-shaped molded piece obtained by hot press-molding a thermoplastic cross-linked resin composition obtained by cutting or cutting.
δ measurement), or a softening temperature measurement such as thermomechanical analysis (TMA) for measuring mechanical displacement due to heating under load, etc. If gives different glass transition temperatures, the highest of those is taken.

In the crosslinked 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. The term "average" as used herein means a value obtained by converting the measured value of birefringence in at least 10 arbitrary points of a given molded product into a value per 1 mm of optical path length by proportional calculation based on the optical path length in the measurement. Therefore, it is desirable that the number of measurement points is as large as possible in terms of reliability of the average value. If the average of the birefringence is too large, the optical distortion of the crosslinked resin composition molded article of the present invention may be too large and may hinder the use as an optical member, so the average value of the birefringence is preferably. 5 nm
Or less, more preferably 3 nm or less, most preferably 2n
m.

In the crosslinked resin composition molded product of the present invention, the standard deviation of the directional anisotropy of the linear expansion coefficient measured as the whole molded product is preferably 10% or less of the average of the linear expansion coefficient. .. The measurement of the coefficient of linear expansion here is performed by, for example, a commercially available thermomechanical analysis (TMA) device. The measurement of the standard deviation of the direction anisotropy of the linear expansion coefficient,
The arithmetic average 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 coefficients. 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 crosslinked resin composition molded article of the present invention may be insufficient as an optical member, so the value of the standard deviation is preferably It is 7% or less, more preferably 5% or less.

In the crosslinked resin composition molded product of the present invention, it is desirable that the average surface roughness Ra is 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.
It is 5 μm or less, more preferably 0.01 μm or less.

When the molded product of the crosslinked resin composition of the present invention contains ultrafine particles containing an inorganic substance, the inorganic substance is a substance having optical characteristics different from that of the resin matrix which is an organic substance. It may have a feature of having a unique refractive index and an Abbe number that cannot be realized. 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. 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 is 1.70 to 1.90.
It means a case that deviates from the range.

[0025]

## EQU1 ## n _D = −0.005 ν _D + C (B) In a transparent resin material, generally, the birefringence increases as the optical path length increases. However, when the above-mentioned ultrafine particles (particularly, ultrafine particles of an inorganic substance) are dispersed in a crosslinked resin matrix, there is a case that the increase rate of birefringence becomes smaller than ever before, despite the increase of the optical path length. Therefore, in a comparatively thick molded body having a thickness of 0.1 mm or more, such a feature is advantageous in terms of lowering the birefringence.

Various additives may be used in combination with the crosslinked resin composition molded article of the present invention as long as the object of the present invention is not 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, fillers such as metal fibers and metal powders, carbon materials such as carbon fibers, carbon black and graphite, antistatic agents, plasticizers, release agents, defoamers, leveling agents, antisettling agents, surfactants , Modifiers such as thixotropy imparting agents,
Colorants such as pigments, dyes, and hue adjusters are exemplified.
In the crosslinked resin composition molded body of the present invention, the addition amount of these various additives is appropriately set depending on the use of the molded body, 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 crosslinked resin composition molded article 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. , Its coating method is vacuum deposition method, CVD
Known coating methods such as a coating 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.
The following is preferably 50 μm or less.

[Polymerizable Liquid Mixture and Polymerizable Monomer] The type of the crosslinked resin forming the main component of the resin matrix of the crosslinked resin composition molding of the present invention is not limited as long as the above-mentioned transparency condition is satisfied. . The raw material of such a crosslinked resin is usually a polymerizable liquid mixture containing a polymerizable monomer having two or more polymerizable functional groups in the molecule as an essential component.

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

Having two or more polymerizable functional groups in the molecule
As a polymerizable monomer that has excellent transparency and low birefringence
Crosslinking A resin having a functionality of 2 or more in terms of giving a crosslinked resin composition
) Acrylates are preferably used. But here
"(Meth) acrylate" means acrylate
Also, it means either methacrylate. Ingredient
Physically, triethylene glycol di (meth) acryl
, Hexanediol di (meth) acrylate, 2,
2-bis [4- (meth) acryloyloxyphenyl]
Propane, 2,2-bis [4- (2- (meth) acrylo]
Iloxyethoxy) phenyl] propane, bis (oxy)
Cimethyl) tricyclo [5.2.1.0^{2, 6}] Decan =
Dimethacrylate, p-bis [β- (meth) acryloyl
Luoxyethylthio] xylylene, 4,4′-bis [β
-(Meth) acryloyloxyethylthio] diphenyl
Divalent (meth) acrylates such as sulfone, trime
Tyrole propane tris (meth) acrylate, glyce
Lintris (meth) acrylate, pentaerythritol
Trivalent (meth) acrole such as rutris (meth) acrylate
Rilates, pentaerythritol tetrakis (meta)
Tetravalent (meth) acrylates such as acrylate, Ure
Indeterminate polyvalent tan acrylate, epoxy acrylate, etc.
(Meth) acrylates and the like are exemplified. These
From the controllability of the cross-linking reaction, the above-mentioned divalent (meth) activator
Relates are preferably used.

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

[0032]

[Chemical 3]

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

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

[0035]

[Chemical 4]

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

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

The ratio of the polymerizable monomer having two or more polymerizable functional groups in the molecule is usually 0.1 to 100 mol% with respect to the total amount of the polymerizable monomers contained in the polymerizable liquid mixture.
The lower limit value is preferably 1 from the viewpoint of dimensional stability and mechanical strength of the crosslinked resin composition produced by the polymerization reaction.
Mol%, and more preferably 3 mol%. Various additives may be added to the polymerizable liquid mixture as long as the produced crosslinked resin composition molded article does not significantly deviate from the object of the present invention. Examples of such additives include stabilizers such as antioxidants, heat stabilizers, or light absorbers,
Fillers such as glass fibers, glass beads, mica, talc, kaolin, clay minerals, metal fibers and metal powders, carbon materials such as carbon fibers, carbon black, graphite, carbon nanotubes, fullerenes such as C ₆₀ , antistatic agents ,
Plasticizer, release agent, defoaming agent, leveling agent, anti-settling agent,
Examples thereof include modifiers such as surfactants and thixotropy imparting agents, pigments, dyes, colorants such as hue adjusters, and the like.

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.
Among these, the semiconductor ultrafine particles impart to the crosslinked resin composition molded article of the present invention functional properties such as light absorption characteristics such as ultraviolet absorption ability, light emission properties, antistatic properties, light absorption saturation properties and high refractive index properties. It is preferable because it has an effect.

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 described later (a two-layer structure of a core as an inner core and a shell as an outer shell containing the core). 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.
(n, exciton) absorption band has not only a very small energy width, but also the exciton level is isolated from the conduction band level and the probability of interaction with adjacent energy levels is relatively small. It is easy to control.

The use of ultrafine particles containing semiconductor crystals having luminescent characteristics makes the crosslinked resin composition molded article of the present invention useful for applications utilizing such luminescent characteristics. In particular,
The emission from the exciton level is particularly useful because the emission band has a small line width and thus the emission has excellent color purity, and the emission wavelength can be controlled by the grain size of the semiconductor crystal due to the quantum effect. 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.

There is no particular limitation on the composition of the semiconductor crystal.
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 such as ZnO, α-Fe ₂ O ₃ , rutile type or anatase type titanium dioxide, and Ce ₂ O ₃ are light absorbing, have a high refractive index, are safe, and are inexpensive. It is most preferable for applications such as ultraviolet absorbing materials and high refractive index coatings. In addition, colored semiconductor crystals having absorptivity in the visible region, such as iron oxides such as α-Fe ₂ O ₃ are important for coloring materials such as pigments.

The most preferable semiconductor crystals for the purpose of making the crosslinked resin composition molded article of the present invention almost colorless and transparent and exhibiting excellent ultraviolet absorbing ability are titanium oxides (typically rutile type or anatase type dioxide). Titanium),
ZnO and Ce ₂ O ₃ . On the other hand, in the case of utilizing the light emitting ability of a semiconductor crystal, II such as GaN, GaP, GaAs, InN, InP, etc. having an emission band in the visible region and its vicinity is used.
Group IV compound semiconductors, ZnO, ZnS, ZnSe, Z
nTe, CdO, CdS, CdSe, CdTe, Hg
II-VI group compound semiconductors such as O and HgS, In ₂ O ₃ , In
₂ S _{3 and the} like are important, and among them, ZnO, ZnS, ZnSe and Z are preferable because of the controllability of the grain size of the semiconductor crystal and the luminous ability.
It is a II-VI group compound semiconductor such as nTe, CdO, CdS, CdSe, and particularly ZnO, ZnS, ZnSe, Cd.
S, CdSe and the like are more preferably used for this purpose.

In any of the semiconductor crystals exemplified above, for example, Al, Mn, Cu, Zn, Zr, A may be added as a trace amount of doping element (meaning impurities intentionally 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 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 prevent or prevent decomposition and deterioration of the resin matrix. It is thought to be to improve stability.

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

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

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

When there are plural kinds of the semiconductor raw material, these may be mixed in advance, or they may be individually injected into the reaction liquid phase. These raw materials may be used as a solution using an appropriate diluting solvent. [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 solution method such as a pulverization method, a precipitation method from a solution, or a method utilizing a reaction in a supercritical liquid. is there. [Organic Ligand] When the ultrafine particles used in the present invention are those in which an organic ligand having compatibility or reactivity with a crosslinked resin matrix is bonded, the ultrafine particles are dispersed in the resin matrix. In some cases, the transparency and interfacial adhesion are dramatically improved, and the transparency and tensile strength of the crosslinked resin composition molded product of the present invention are dramatically improved. The binding of the above organic ligand may improve electromagnetic properties such as absorption and emission ability of the ultrafine particles. This is because the surface of the light absorbing and emitting inorganic ultrafine particles such as semiconductor nanocrystals is organically coordinated. It is considered that this is due to a mechanism in which the contribution of unfavorable impurity levels, lattice defect levels, etc. is reduced by the bond of the child.

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 the molecular weight is too large, various physical properties of the crosslinked resin matrix, particularly mechanical properties (tensile strength, elastic modulus, heat resistance, etc.) may be impaired. Although the molecular weight may have a distribution, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn is usually 1 to 10 in view of the role of the organic ligand,
It is preferable to control to 1 to 7, more preferably 1 to 5, and most preferably 1 to 3.

The above-mentioned reactivity of the organic ligand with respect to the resin matrix means the reactivity for giving a state in which a bond is formed between the organic ligand and the polymer constituting the crosslinked resin matrix. To do. To provide such a state, the reaction between the organic ligand bound to the ultrafine particles and the polymerizable monomer that gives the polymer forming the crosslinked resin matrix (copolymerization reaction with the polymerizable monomer may be used) And, the polymerization reaction of the polymerizable monomer to be allowed to proceed next is possible. For these methods, see also the description in the section "Process for producing molded article of crosslinked resin composition".

The effect of the binding of the organic ligand 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 crosslinked 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.

[0060]

Embedded image where X represents a functional group that forms an arbitrary chemical bond (eg, covalent bond, ionic bond, coordination bond, hydrogen bond, etc.) with the surface of the ultrafine particles, and Y Represents a functional group having compatibility or reactivity with the crosslinked 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 used, and 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

Regarding the functional group Y, when it is a functional group having reactivity with the crosslinked resin matrix,
Nucleophilic or electrophilic substitution reactive functional groups such as hydroxyl group, amino group, carboxyl group, ester group, amide group, acryloyl group, methacryloyl group, maleoyl group, vinylphenyl group, vinyl ester group, vinylamino group, ethynyl group, etc. The radically polymerizable group and the like are exemplified.

Among the examples of the above-mentioned functional group Y, the amino group is rich in a bond derived from a carboxyl group such as an ester bond, a carbonate bond, an amide bond and the like, and has a nucleophilic substitution reactivity with an epoxy group. It is suitable for application to a crosslinked resin matrix mainly composed of a crosslinked resin containing a carbonate bond, an amide bond and an epoxy group (for example, acrylic resin, polyester resin, polycarbonate resin, polyamide resin, epoxy resin, etc.). 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 crosslinked 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 crosslinked resin matrix, its chemical structure is part of the chemical structure of the repeating unit of the polymer which is the main constituent of the crosslinked resin matrix. Alternatively, it is preferably the same as or similar to all. 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 world. From the viewpoint, the lower limit is preferably 3 or more, more preferably 6 or more, further preferably 9 or more, on the other hand, for the purpose of not significantly reducing the heat resistance and mechanical strength of the crosslinked resin composition molded product of the present invention. It is preferably 25 or less, more preferably 20 or less.

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

[0067]

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

[0068]

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.

[0069]

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

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

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

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

The specific coordination chemical structure of the above-mentioned organic ligand on the surface of inorganic ultrafine particles such as semiconductor crystals is determined by NMR or XAF.
Although there have been examples of studies by analytical methods such as S, they have not been sufficiently clarified, but in the present invention, the functional group X in the general formula (3) does not necessarily have to retain the structure as it is. For example, in the case of a mercapto group (SH), a transition metal element M 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 Crosslinked Resin Composition Molded Article] The method for producing the crosslinked resin composition molded article of the present invention is not limited,
For example, 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 enhance 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 for this is not clear, but it is presumed that the initiation of the polymerization reaction is homogeneous in the polymerization system and progresses in a short period of time due to the homogeneity of the product. 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-mentioned 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 the active energy ray or the irradiation time is extremely short, the heat resistance, dimensional stability, or mechanical properties of the obtained crosslinked resin composition molded article may not be sufficiently expressed due to incomplete polymerization, and vice versa. If it is extremely excessive, deterioration such as yellowing may occur, which is represented by deterioration of hue due to light. The temperature condition during irradiation with the active energy rays is preferably 70 ° C. or lower. 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 carried out by a method in which the polymerizable liquid mixture and the light source are fixed and left stationary or while the former is transferred by a conveyor or the like. 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 crosslinked 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 molded article of the crosslinked resin composition of the present invention has excellent optical properties (transparency, dimensional stability, isotropic optical or dimensional stability, low optical strain, and ultraviolet rays of dispersed semiconductor nanocrystals. It is preferably used for an optical member that transmits light (so-called passive optical member) due to its absorption property (UV resistance, etc.) and tensile strength. 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. Examples of such optical functional devices are various display devices (liquid crystal displays, plasma displays, etc.), various projector devices (OHP, liquid crystal projectors, etc.), optical fiber communication devices (optical waveguides, optical amplifiers, etc.), cameras, video shooting devices, etc. Is exemplified.

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

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

[0082]

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.

Purified toluene: Concentrated sulfuric acid, water, saturated aqueous sodium hydrogen carbonate, and then water in that order, dried over anhydrous magnesium sulfate, filtered through filter paper, and added diphosphorus pentoxide (P ₂ O ₅ ) to give a large volume. Distilled at atmospheric pressure. Purified methanol: dried with calcium sulfate and calcium hydride, further added with sodium hydride, and distilled directly from here at atmospheric pressure,
Or anhydrous ("Anhy" supplied by Aldrich).
druse ") grade 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) Light transmittance and absorption spectrum: Hewlett-Packard
HP-8453 type UV / Visible absorptiometer manufactured by KK
It was measured at room temperature. Light transmittance measurement of crosslinked resin composition moldings
1mm thick test piece is used for measurement
And the arithmetic mean value was used for the following evaluation. (7) Pyrolysis residue rate: A part of the crosslinked resin composition molded body is taken
And take thermogravimetric analysis (TG) to 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) Glass transition temperature: heat resistance: 3 mm x 30 mm x
Using a 0.5 mm strip-shaped test piece, the glass transition temperature T
g was measured by a tensile method TMA with a weight of 2 g. Temperature rise
The condition was 5 ° C./min. (9) Birefringence: using a crosslinked resin composition molded body with a thickness of 1 mm
Automatic birefringence measuring device (Oak Seisakusho, ADR-1
50 N) at 25 ° C. Measurement is any different
10 points, and use the arithmetic mean value for the following evaluation
It was (10) Crackability test (simple evaluation of tensile strength or elastic modulus
Value): As a qualitative simple evaluation of mechanical strength, molded products
We compared the magnitude of the force required to bend and break by hand. small
If it is easy to break even with strong force, it will be ×, if it is hard to break, it will be ○, both
The middle of the cases was evaluated as Δ, and a three-level evaluation was performed.

[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).

[0086]

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).

Synthesis Example 3: Core-shell structure CdSe ultrafine particles having ZnS shell B. 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 CdSe ultrafine particles having MTEG-C11SH as an organic ligand 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 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 product of
The light transmittance at 50 nm wavelength (denoted as D-ray transmittance and 350 nm transmittance, respectively, unit:%), the glass transition temperature (unit: ° C.), the birefringence (unit: n).
m), the brittleness test, and the pyrolysis residue rate (unit:%) were evaluated, and the results are summarized in Table-1. It should be noted that the sheet-shaped molded products of any of the examples were ASTM-D using themselves.
The tensile strength measured according to the 638 standard is 1 MPa or more.

Example 1: TiO₂A rack containing ultrafine particles
Bridge Acrylic crosslinked resin composition For thermal radical polymerization of molded products
Preparation by The dialkyl sulfosuccinate obtained in Synthesis Example 5 was organically distributed.
TiO as a unit₂7 parts by weight of ultrafine particles, bis (hi
Droxymethyl) tricyclo [5.2.1.0^{2 , 6}] De
Can = dimethacrylate 93 parts, as a heat radical generator
Azobisisobutyronitrile (commonly known as AIBN)
Dissolve 1 part by volume in a mixed solvent of ethyl acetate and n-hexane
A clear solution was obtained. Solvent (ethyl acetate and n-hexa
Of the polymerizable liquid mixture obtained by distilling
Is between 0.004 μm and the space between two stainless steel plates.
In the gap between stainless steel plates with a thickness of 1 mm
Pour and heat in a dry nitrogen atmosphere at approx.
And allow it to heat up at 120 ° C for 40 minutes.
To form a transparent sheet-like crosslinked resin composition having a thickness of 1 mm.
I got a shape. This sheet-like cross-linked tree was observed by the above TEM.
When the fat composition molded body was analyzed,₂Ultra fine particles
The primary particles of the child are dispersed in a substantially non-aggregated state,
No ultrafine particles having a diameter of 60 nm or more were observed. this
The sheet-shaped crosslinked resin composition molded body is made of toluene or chlorophore.
Rum, acetone, tetrahydrofuran
Even if it tries to dissolve, it is practically insoluble.₂Superfine
It had an ultraviolet absorbing ability derived from particles.

Example 2: Preparation of crosslinked crosslinked resin composition containing TiO ₂ ultrafine particles by photoradical polymerization 45 parts by weight of TiO ₂ ultrafine particles having the dialkyl sulfosuccinate obtained in Synthesis Example 5 as an organic ligand , Bis (hydroxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane = dimethacrylate 45 as a 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-like crosslinked resin composition molded product having a thickness of 1 mm. When the sheet-like crosslinked resin composition molded body 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 observed. Was not done. This sheet-shaped crosslinked resin composition molded article 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. .

[Comparative Example] The same evaluation as in the above-mentioned example was carried out. The results are summarized in Table-1. Comparative Example 1: Crosslinked Resin Molded Body Not Containing Ultrafine Particles The same operation as in Example 1 was carried out without mixing the TiO ₂ ultrafine particles to obtain a sheet-shaped molded body having a thickness of 1 mm.

Comparative Example 2: Use of Non-Crosslinked Resin Matrix Polymethylmethacrylate (manufactured by Tokyo Kasei Co., Ltd .; average molecular weight: 7 to 75,000; hereinafter referred to as PMMA) 93 parts of propylene glycol monoethyl ether acetate (hereinafter referred to as PMMA) It is dissolved in 400 parts of PEG MEA) at 40 ° C. with stirring, and then 7 parts by weight of TiO ₂ ultrafine particles having the dialkylsulfosuccinate obtained in Synthesis Example 5 as an organic ligand is added, and the mixture is further stirred for 2 hours to homogenize it. To obtain a polymerizable liquid mixture. After half the PEGMEA was removed by evaporation using an evaporator, this polymerizable liquid mixture was applied onto a glass substrate by the bar coating method and dried at 120 ° C. to obtain a thin film. Bar coating was further applied onto the thin film, and the same operation was repeated thereafter to obtain an ultrafine particle-dispersed PMMA sheet having a thickness of 1 mm. The sheet-shaped crosslinked resin composition molded body was dissolved in toluene, chloroform and tetrahydrofuran.

Comparative Example 3: Crosslinked Resin Composition Molded Article Containing Ultrafine Particles with Large Particle Size In Example 1, TiO ₂ ultrafine particles supplied from CI Kasei Co., Ltd. as titanium oxide ultrafine particles (average particle diameter by BET method) (Diameter 30 nm) was used and compounded so as to have an equivalent rate of thermal decomposition residue, and the same operation was performed to obtain a PC resin sheet-shaped molded product having a thickness of 1 mm. The cross-linked resin composition molded body thus obtained was visually opaque, and
When this sheet-shaped resin composition molded body was analyzed by M observation, TiO ₂ ultrafine particles having a particle size of 60 nm or more accounted for about 12% by volume in all the ultrafine particles. 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.

[0097]

[Table 1]

[0098]

EFFECTS OF THE INVENTION Since the crosslinked resin composition molded product of the present invention contains ultrafine particles uniformly dispersed therein, it has high transparency and excellent tensile strength or elastic modulus. When the ultrafine particles have an ultraviolet absorbing property, they retain their characteristics and thus have excellent ultraviolet resistance. In addition, it also has the effect that the optical distortion evaluated by birefringence is small.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 33/04 C08L 33/04 G02B 1/04 G02B 1/04 G02F 1/1335 G02F 1/1335 // C09K 3/00 104 C09K 3/00 104Z F-term (reference) 2H091 FA21X FA21Z FA23Z FA26X FA26Z FB02 LA30 4F071 AA03 AA86 AB18 AD02 AE17 AF29 AF30 AH12 4J002 BG031 FB061 FB061 FB036 FB061 006 006DH036 DA056DA046 FB146 FB156 FB196 FB236 FD016 GP01 GP02 GQ05 4J027 AA02 BA07 BA24 CA12 CA13 CA14 CA15 CA16 CA17 CA18 CA36 CB09 CB10 CC02 CD03 CD04 CD05 4J100 AL62P AL63P AL66P BA02P BA12P BA51P BA58P BC08P BC12P BC43P DA43

Claims (14)

[Claims] 1. A crosslinked resin composition in which ultrafine particles having a number average particle diameter of 0.5 to 50 nm are dispersed and which has a tensile strength of 1 MPa or more, and an optical path length of 1 at a sodium D-line wavelength.
A crosslinked resin composition molded article having an average light transmittance per mm of 70% or more and a minimum thickness of 0.1 mm or more. 2. The crosslinked resin composition molded article according to claim 1, wherein the ultrafine particles contain an inorganic material. 3. The crosslinked resin composition molded article according to claim 2, wherein the ultrafine particles contain semiconductor crystals. 4. The semiconductor crystal is any one of a titanium oxide crystal, a zinc oxide crystal and a cerium oxide crystal.
The cross-linked resin composition molded article according to 1. 5. The residue obtained by pyrolyzing for 120 minutes at 600 ° C. in a nitrogen atmosphere has a weight of 1 to 6 before the pyrolysis.
It is 0%, The crosslinked resin composition molded body in any one of Claims 1-4. 6. The crosslinked resin composition molded article according to claim 1, wherein the proportion of the ultrafine particles having a particle size of 60 nm or more is 10% by volume or less based on the volume of all the ultrafine particles. 7. The average of the light transmittances per 1 mm of the optical path length at a wavelength of 350 nm is 50% or less.
The crosslinked resin composition molded article according to any one of 6 above. 8. The crosslinked resin composition molded article according to claim 1, which has a glass transition temperature of 150 ° C. or higher. 9. The average birefringence per 1 mm of optical path length is 1.
The crosslinked resin composition molded body according to any one of claims 1 to 8, which has a thickness of 0 nm or less. 10. The crosslinked resin composition molded article according to claim 1, wherein the ultrafine particles are bonded with an organic ligand. 11. The crosslinked resin composition molded article according to claim 1, wherein the crosslinked resin composition is obtained by polymerizing a polymerizable liquid mixture containing a polymerizable monomer. 12. The crosslinked resin composition molded article according to claim 11, wherein the polymerizable monomer is mainly composed of the following general formulas A and / or B. Component (A): an alicyclic skeleton bis (meth) acrylate represented by the following general formula (1). [Chemical 1] (In the general formula (1), R ^a and R ^b are each independently a hydrogen atom or a methyl group, R ^c and R ^d are each independently an alkylene group having 6 or less carbon atoms, and x is 1 or 2 And y represents 0 or 1, respectively.) Component (B): a bis (meth) acrylate having a sulfur atom represented by the following general formula (2). [Chemical 2] (In the general formula (2), R ^a and R ^b are the same as in the general formula (1), R ^e is 6 carbon atoms, respectively representing. Each Ar represents an alkylene group having 1 to 6 carbon atoms It represents an arylene group or an aralkylene group which is 30, and these hydrogen atoms may be substituted with a halogen atom other than fluorine, each X represents an oxygen atom or a sulfur atom, and when each X is an oxygen atom, At least one of each Y has a sulfur atom or a sulfone group (—SO ₂ —)
When at least one of them is a sulfur atom, each Y is a sulfur atom, a sulfone group, a carbonyl group (—CO—),
And an alkylene group having 1 to 12 carbon atoms, an aralkylene group, an alkylene ether group, an aralkylene ether group,
Represents either an alkylene thioether group or an aralkylene thioether group, and j and p are each independently 1
Is an integer of 5 and k is an integer of 0-10. K is 0
Then X represents a sulfur atom. ) 13. The polymerizable liquid mixture is cured by heat or active energy rays.
Or the method for producing a crosslinked resin composition molded article according to item 12. 14. An optical member comprising the crosslinked resin composition molded article according to claim 1.