JP2002214139A - Analytical method and analytical device of phase separation structure using semiconductor ultrafine particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for analyzing a phase separation structure by performing selective detection of a specific phase in the phase separation structure in the bulk state, including the change with age according to need. SOLUTION: Semiconductor ultrafine particles having reinforced compatibility with the specific phase in a phase separation system are allowed to coexist in the phase separation system, and the semiconductor ultrafine particles are detected by a confocal microscope.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for analyzing a phase separation structure by detecting semiconductor ultrafine particles with a confocal microscope. The analysis method and apparatus according to the present invention detect semiconductor ultrafine particles unevenly distributed in a specific phase in a phase separation system using a confocal microscope and visualize the distribution as a three-dimensional image. In addition to the research and development of new multiphase materials that require a high degree of control, industrial applications that need to track the phase separation process in the liquid phase, especially during the polymer formation process of polymerizable monomers,
For example, it is used for manufacturing process management of a new multiphase material manufactured by such a process.

[0002]

2. Description of the Related Art An example in which semiconductor ultrafine particles are localized in a specific phase of a phase-separated polymer multicomponent system and analyzed is disclosed in WO
It is known from JP 98/35248. That is, in Example 2, nanocrystals of cadmium selenide (CdSe) having trioctylphosphine oxide (TOPO) as an organic ligand were obtained by using poly (2-vinylpyridine) (P2VP), polyisoprene, and polystyrene.
It has been confirmed by transmission electron microscope (TEM) observation that CdSe nanocrystals are unevenly distributed in the phase-separated P2VP domain when dispersed in the original block copolymer matrix. However, TEM observations are generally limited to thin-film samples, so in the case of bulk samples, it is not only necessary to cut them out into flakes, but also to analyze the phase structure fixed as a solid phase, It was virtually impossible to analyze the separation process.

On the other hand, three-dimensional image analysis of the internal structure of a bulk sample using a confocal microscope is possible by incorporating a luminescent substance such as an organic dye into the sample, exciting the dye, and observing the luminescence. However, when an attempt is made to analyze the phase separation process caused by concentration and polymer formation from a homogeneous liquid phase by such a method, for example, since organic dyes are generally low molecular weight compounds, the solubility difference in each phase generated in the phase separation process is high. Is relatively small, and it is generally difficult to control or design the staining of only a specific phase, particularly the staining of a separated phase due to the formation of a polymer, depending on the structure of the dye molecule.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to selectively detect a specific phase in a phase-separated structure in a bulk state, if necessary. An object of the present invention is to provide a method and an apparatus for analyzing the phase-separated structure by performing the method including changes over time.

[0005]

Means for Solving the Problems The present inventors add a semiconductor ultrafine particle whose surface chemical structure is controlled by an organic ligand to a process for producing a polymer from a liquid phase containing a polymerizable monomer. By considering that it is possible to unevenly distribute the semiconductor ultrafine particles in a specific phase of the phase separation structure generated by the polymer generation process, and systematically conducted a study of observing the emission with a confocal microscope, Phase separation structure 3
The present inventors have found that they can be observed as a two-dimensional image, and arrived at the present invention.

That is, a first gist of the present invention is to make semiconductor ultrafine particles having enhanced compatibility with a specific phase in a phase separation system coexist in the phase separation system and detect the semiconductor ultrafine particles by a confocal microscope. And a method for analyzing a phase separation structure. A second gist of the present invention resides in an apparatus for analyzing a phase separation structure using the above-described analysis method, wherein the confocal microscope is equipped with a transparent container used for observation of a liquid phase sample.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Phase Separation System and Its Analysis Principle] The method for analyzing a phase separation structure according to the present invention comprises adding a semiconductor ultrafine particle described later to an arbitrary phase separation system and converting the semiconductor ultrafine particle into a specific phase. And to detect its presence due to enhanced compatibility. The “enhanced compatibility with a specific phase” as used herein is mainly controlled by the chemical structure of the surface of the semiconductor ultrafine particles, particularly the chemical structure of an organic ligand described later.

The phase separation system which is the object of the analysis method of the present invention comprises a condensed phase, ie, a liquid phase and / or a solid phase, and its constituent materials are not limited. (Void) may be contained. A typical phase separation system targeted by the analysis method of the present invention is, for example, a polymer phase separation system as described later.
The liquid phase means a condensed phase capable of viscous flow, the viscosity is not limited, and the liquid phase may contain a dispersed solid phase. The phase separation system has either a separation structure of different composition phases or a separation structure of different phases having the same composition (for example, a combination of complementary different phases such as a liquid phase and a solid phase, or an amorphous phase and a crystal phase). No problem. Further, the phase separation system includes:
A fixed state that does not substantially change spatial phase morphology (hereinafter, referred to as “morphology”) for at least a time range of several minutes to several days (for example, a thermodynamically stable state that is left standing in a solid container, Liquid in a metastable state, a thermodynamic non-equilibrium state fixed to a solid phase, etc.) or a non-equilibrium state in which a morphological change occurs within a relatively short time period of several minutes or less.

The core of the effect of the present invention lies in the use of ultrafine semiconductor particles as an analysis probe. Since the semiconductor ultrafine particles to be described later usually have a particle size of several nanometers (nm) and preferably have a luminous ability, it is very suitable to observe such luminescence in the present invention. Also,
Since it is a much larger object than the conventional low molecular dyes, the entropy effect of mixing with the medium molecules makes the selectivity of the mixable medium, that is, the selectivity of the compatibility with the medium low molecular solute. It is much larger than. For this reason, the selective detection of a specific phase in the phase separation structure, which is the object of the present invention, is achieved very effectively.

In the analysis method of the present invention, the semiconductor ultrafine particles added to the target phase separation system are detected by a confocal microscope described later. There is no limitation on the mechanism of such detection,
Usually, electromagnetic properties such as light emission, light absorption (or coloring) of the semiconductor ultrafine particles, or a difference in refractive index from the matrix are detected. Among them, light emission is preferable in terms of detection sensitivity, and light emission at a specific wavelength is preferable. In terms of luminous efficiency, it is more preferable to use a luminous band derived from an exciton level due to a quantum effect of semiconductor ultrafine particles.

Although there is no limitation on the process of generating the phase separation system which is the object of the analysis method of the present invention, it is necessary to add the ultrafine semiconductor particles before the completion of the phase separation. This is because the semiconductor ultrafine particles are unevenly distributed due to enhanced compatibility with a specific phase generated in the phase separation process.
The “state before completion of phase separation” as used herein refers to an initial state of the phase separation process, for example, (1) a polymerizable phase in which a non-uniform phase (eg, a molecular orientation phase such as a crystalline phase and an amorphous phase) is formed by increasing the molecular weight. A monomer or a solution thereof, (2) a solution of a single polymer that produces a heterogeneous phase as described above by concentration and removal of the solvent, (3)
Homogeneous solution of heterogeneous solute (typically heterogeneous polymer), (4)
A melt-mixed raw material of a different substance (for example, a mixture of resin pellets of a different polymer that is a raw material in a melt polymer blending step by an extruder) or the like, or a phase in the process of phase separation starting from these initial states, that is, the above-mentioned polymerization, concentration, It means a state in the middle of melting and mixing. Regarding the timing of adding the semiconductor ultrafine particles, the addition in the initial state described above is preferable from the viewpoint of the sensitivity of phase separation detection, particularly the contrast (S / N ratio).

The analysis method of the present invention exhibits particularly excellent characteristics when the target phase separation system contains a polymer. This is because a polymer generally has a lower ability to dissolve a solute than a corresponding polymerizable monomer due to its entropy effect, and the selectivity of compatibility with a solute present in a system, that is, a semiconductor ultrafine particle, is low. This is because it increases more than the separation system. In other words, when the target phase separation system contains a polymer, the difference in compatibility of the semiconductor ultrafine particles contained in each phase tends to increase.

Another case where the analysis method of the present invention particularly exhibits its excellent features is in-situ analysis of the phase separation process of the phase separation system of interest. The reason for this is that a conventional phase separation structure analysis technique, for example, the TEM
This is because, in observation and the like, the phase separation structure is usually limited to a solid phase sample having a fixed phase separation structure. By collecting a temporal analysis image of a phase separation process using a confocal microscope described later, accurate three-dimensional image analysis can be easily performed.

[Semiconductor Ultrafine Particles] The above semiconductor ultrafine particles are mainly composed of semiconductor crystal particles to be described later and usually have an organic ligand bonded to the surface thereof. The chemical structure of the surface of the semiconductor ultrafine particles is a main factor for controlling the affinity with the phase for the purpose of uneven distribution thereof (hereinafter, referred to as “uneven target phase”), that is, the interface free energy. Qualitatively,
It is preferable to improve the affinity between the chemical structure of the unevenly distributed target phase and the chemical structure of the surface of the semiconductor ultrafine particles. An effective means for controlling and improving the affinity is to bond an organic ligand described below to the surface of the semiconductor crystal particle and control the chemical structure thereof.

Two methods are exemplified as a strategy for controlling the chemical structure of the organic ligand. The first is to make the chemical structure of the organic ligand similar to the chemical structure of the unevenly distributed target phase, that is, to make the mixing enthalpy of both structures as small as possible. Second, in the phase separation system generation process (including the initial state), molecules constituting the unevenly distributed target phase (hereinafter referred to as “dispersed phase molecules”, which may be polymers) and the organic ligand Is to design the formation of chemical bonds by the reaction with According to the second method, the structure of the dispersed phase molecule is introduced into the surface of the semiconductor ultrafine particles via the organic ligand, whereby the effect of the first method is exhibited. Such an organic ligand will be described later in detail.

The semiconductor crystal particles which are the main components of the semiconductor ultrafine particles used in the present invention are particles containing an arbitrary semiconductor crystal, and the structure and composition of the semiconductor crystal are, for example, a semiconductor single crystal and a plurality of semiconductor crystals. Either a mixed crystal having a phase separated composition or a mixed semiconductor crystal having no phase separation observed may be used. In addition, the semiconductor crystal particles may have a core-shell structure described later.

The number average particle size of the semiconductor crystal particles in the present invention is usually 0.5 to 50 nm, preferably 1 to 30 n.
m, more preferably 2 to 20 nm, most preferably 3 to
It is about 10 nm. For the determination of the number average particle size of the semiconductor crystal particles, a numerical value measured from a transmission electron microscope (TEM) observation image of a given phase separation system is used. That is,
The diameter of a circle having the same area as the observed semiconductor crystal particle image is defined as the particle size of the particle image. The number average particle diameter is calculated using the particle size determined in this way, for example, by a known statistical processing method of image data. The number of semiconductor crystal particle images (the number of statistical processing data) used in the statistical processing is as large as possible. It is naturally desirable that the number of the particle images is at least 50, preferably at least 80, more preferably at least 100 in the present invention. If the number average particle size is too large, the selectivity of compatibility with the unevenly distributed target phase may be deteriorated or the luminous ability derived from the exciton level due to the quantum effect may not be remarkable. If the particle size is too small, the function of the semiconductor crystal particles as an independent crystal (for example, formation of a band structure giving light emitting ability) may be reduced, and both are not preferred.

The smaller the particle size distribution of the semiconductor crystal particles determined as described above, the higher the selectivity of compatibility with the unevenly distributed target phase and the absorption band or emission band based on the exciton level. This is preferable because an effect such as a reduction in the wavelength width can be considered. Therefore, the particle size distribution usually has a standard deviation of 20% or less, preferably 15% or less.
Hereafter, it is more preferably controlled to 10% or less.

The semiconductor ultra-fine particles used in the present invention may be used in combination of two or more kinds, or even if the semiconductor ultra-fine particles are composed of the same kind of semiconductor crystal, the particle size distribution such as a double peak distribution can be optionally determined. You can change it to However, from the viewpoint of optical transparency in confocal microscopy observation, that is, reduction of light scattering, it is desirable that semiconductor crystal particles having a particle size exceeding 100 nm are not contained.

[Addition amount of semiconductor ultrafine particles] The amount of semiconductor ultrafine particles added to the target phase separation system in the analysis method of the present invention is not limited as long as it can be detected. Although it varies depending on the fraction, the abundance of the semiconductor crystal particles is usually 0.001 to 30% by volume of the entire phase separation system including the semiconductor ultrafine particles, and preferably 0.01 to 20% by volume in terms of detection efficiency. %, More preferably about 0.1 to 10% by volume.

The added amount of the semiconductor ultrafine particles can be calculated from the content of the remaining semiconductor composition and the specific gravity thereof by thermogravimetric analysis of a given phase separation system. Such thermogravimetric analysis is carried out with good reproducibility by elevating the temperature from room temperature to about 600 ° C. in an inert gas stream such as a nitrogen stream and keeping the temperature at this temperature for about 120 minutes to thermally decompose the organic components. You.

Another method for determining the amount of semiconductor ultrafine particles to be added is a transmission electron microscope (TE) of a given phase separation system.
M) A numerical value measured from an observation image is used. That is, the diameter of a circle having the same area as the observed semiconductor crystal particle image is defined as the particle size of the particle image, and the volume of a sphere having the same diameter as the particle size is defined as the volume of the crystal particle. Using the volume of each particle determined in this way, the volume percentage is calculated by, for example, a known statistical processing method of image data. However, the number of semiconductor crystal particle images (the number of statistical processing data) used in the statistical processing is acceptable. Naturally, it is desirable that the number of the particle images is at least 50 or more, preferably 80 or more, and more preferably 1 or more.
00 or more.

[Composition of Semiconductor Crystal] The above-mentioned semiconductor crystal grains
Although there is no particular limitation on the composition of the semiconductor crystal contained in the
For the purpose of the present invention, properties such as absorption and emission characteristics and high refractive index
It is desirable that the semiconductor crystal has a quality. Such semiconduct
Example of composition of body crystal is shown as element symbol or composition formula
Then, the elements of Group 14 elements of the periodic table such as C, Si, Ge, and Sn
Simple substance, simple substance of Group 15 element of the periodic table such as P (black phosphorus), S
e, Te, and other simple elements of Group 16 elements of the periodic table,
Consisting of elements of group 14 of the periodic table, SnO_Two, S
n (II) Sn (IV) S_Three, SnS_Two, SnS, SnSe,
Periodic table first such as SnTe, PbS, PbSe, PbTe
Compound of Group 4 element and Group 16 element of the periodic table, BN, B
P, BAs, AlN, AlP, AlAs, AlSb, G
aN, GaP, GaAs, GaSb, InN, InP,
Group 13 elements of the periodic table such as InAs and InSb
Compounds with Group 15 elements (or III-V compounds)
Body), Al_TwoS_Three, Al_TwoSe _Three, Ga_TwoS_Three, Ga_TwoSe_Three,
Ga_TwoTe_Three, In_TwoO_Three, In_TwoS_Three, In_TwoSe_Three, In_Two
Te_ThreeGroup 13 elements of the periodic table and group 16 elements of the periodic table
Of the Periodic Table of the Compounds TlCl, TlBr, TlI, etc.
Compound of Group 3 element and Group 17 element of the periodic table, ZnO, Z
nS, ZnSe, ZnTe, CdO, CdS, CdS
periodic table of e, CdTe, HgS, HgSe, HgTe, etc.
Compounds of Group 12 elements and Group 16 elements of the periodic table (or
Is a II-VI compound semiconductor), As_TwoS_Three, As_TwoS
e_Three, As_TwoTe_Three, Sb_TwoS_Three, Sb_TwoSe_Three, Sb_TwoT
e_Three, Bi_TwoS_Three, Bi_TwoSe_Three, Bi_TwoTe_ThreePeriodic Table No.
Compound of Group 15 element and Group 16 element of periodic table, Cu
_TwoO, Cu_TwoGroup 11 elements of the periodic table, such as Se, and 16 of the periodic table
Compound with group elements, CuCl, CuBr, CuI, Ag
Group 11 elements of the periodic table, such as Cl and AgBr, and elements of the periodic table 17
Compounds with Group 10 elements, Periodic Table 10 elements such as NiO
Period of compounds with Group 16 elements, CoO, CoS, etc.
A compound of a Group 9 element of the Table and a Group 16 element of the Periodic Table, Fe_Three
O_Four, FeS and other elements of group 8 of the periodic table and elements of group 16 of the periodic table
Compounds of the Periodic Table with elements of Group 7 of the Periodic Table such as MnO
Compound with Group 16 element, MoS_Two, WO_TwoPeriodic Table 6
Compounds of group 16 elements and elements of group 16 of the periodic table, VO, V
O_Two, Ta_TwoO_FiveAnd other elements of group 5 of the periodic table
Compound with element, TiO_Two, Ti_TwoO_Five, Ti_TwoO_Three, Ti_Five
O₉Titanium oxides (crystal type is rutile type, rutile / a
It does not matter whether it is a mixed crystal or anatase type of natase.
I), ZrO_TwoOf the Periodic Table Group 4 and the Periodic Table Group 16
Compounds with elements, elements of the second group of the periodic table such as MgS and MgSe
Compound of element and element of group 16 of the periodic table, CdCr_TwoO_Four, C
dCr_TwoSe_Four, CuCr_TwoS_Four, HgCr _TwoSe_FourEtc. Cal
Cogen spinel or BaTiO_ThreeEtc.
You. G. Schmid et al .; Adv. Mate
r. , Vol. 4, p. 494 (1991).
(BN)₇₅(BF_Two)₁₅F₁₅And D. Fenske et al .;
Angew. Chem. Int. Ed. Engl. , 2
9, 1452 (1990).
₁₄₆Se₇₃(Triethylphosphine)_{twenty two}Like structure
Semiconductor clusters that have been determined are also exemplified.

Of these, those which are practically important are, for example, SnO ₂ , SnS ₂ , SnS, SnSe, SnTe, P
Compounds of Group 14 element and Group 16 element such as bS, PbSe, PbTe, etc., GaN, GaP, GaAs
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, In ₂ Te periodic table Group 13 element ₃ or the like and the Periodic Table 1
Compounds with Group 6 elements, ZnO, ZnS, ZnSe, Zn
Te, CdO, CdS, CdSe, CdTe, HgO,
HgS, HgSe, II-VI group compound semiconductor such as _{HgTe, As 2 O 3, As} 2 S 3, As 2 Se 3, As 2 Te 3,
Sb ₂ O ₃ , Sb ₂ S ₃ , Sb ₂ Se ₃ , Sb ₂ Te ₃ , Bi ₂
Compounds of Group 15 elements and Group 16 elements such as O ₃ , Bi ₂ S ₃ , Bi ₂ Se ₃ , and Bi ₂ Te _3, and compounds of the Periodic Table 4 such as the above-mentioned titanium oxides and ZrO ₂ . It is a compound of a group 16 element and a group 16 element of the periodic table, and a compound of a group 2 element of the periodic table such as MgS and MgSe and a group 16 element of the periodic table.

Among these, SnO_Two, GaN, Ga
P, In_TwoO_Three, InN, InP, Ga_TwoO_Three, Ga_TwoS_Three,
In_TwoO_Three, In_TwoS_Three, ZnO, ZnS, CdO, Cd
S, the above-mentioned titanium oxides and ZrO_Two, MgS, etc. have high bending
With a high refractive index and no highly toxic negative elements
It is preferable in terms of environmental pollution and safety to living organisms.
Then SnO_Two, In_TwoO_Three, ZnO, ZnS, oxidation as described above
Titanium and ZrO_TwoDoes not contain highly toxic positive elements such as
The composition is more preferable, among which ZnO or the above-mentioned acid
Titanium chlorides (rutile crystals are particularly preferred for high refractive index
Preferred) and ZrO _TwoOxide semiconductor crystals such as
New

On the other hand, GaN, GaP, GaAs, InN and
III-V compound semiconductors such as InP, ZnO, ZnS,
ZnSe, ZnTe, CdO, CdS, CdSe, Cd
II-VI compound semiconductors such as Te, HgO, and HgS;
In ₂ O ₃ , In ₂ S _{3 and the} like are important, and among them, ZnO, Zn
II-VI compound semiconductors such as S, ZnSe, ZnTe, CdO, CdS, and CdSe;
dS, CdSe, etc. are more preferably used for this purpose.

The composition of any of the semiconductor crystals exemplified above may include, for example, Al, Mn, Cu, Zn, A as a small amount of a doping material (meaning the intentionally added impurity) as necessary.
g, Cl, Ce, Eu, Tb, Er and the like may be added.
In some cases, such as S: Mn and ZnS: Tb (where the element after “:” is a doping substance), a preferable luminous ability in a visible region or the like is provided.

[Semiconductor crystal particles having core-shell structure]
The semiconductor crystal particles are, for example, A.I. R. Kortan
J. et al. Am. Chem. Soc. , 112, 132
As reported in page 7 (1990) or US Pat. No. 5,985,173 (1999), a so-called core-shell structure comprising an inner core and an outer shell is used for the purpose of improving the electronic excitation characteristics of the semiconductor crystal. Then
Since the stability of the quantum effect of the semiconductor crystal forming the core may be improved in some cases, the semiconductor crystal is suitable for using the above-described absorption band or emission band based on the exciton level. In this case, it is generally effective to form an energy barrier by using a semiconductor crystal having a band gap larger than that of the core as a composition of the semiconductor crystal of the shell. This is presumed to be due to a mechanism for suppressing the influence of an undesirable surface level or the like due to the influence of the outside world or a crystal lattice defect on the crystal surface.

The composition of the semiconductor crystal suitably used for such a shell depends on the band gap of the core semiconductor crystal.
At least 2.0 eV, for example, B
N, BAs, III-V compound semiconductors such as GaN and GaP, ZnO, ZnS, ZnSe, ZnTe, CdO, C
II-VI group compound semiconductors such as dS, MgS and MgSe
Compounds of the Group 2 elements of the Periodic Table and the Group 16 elements of the Periodic Table, etc. are preferably used. Among these, a semiconductor crystal composition that is a more preferable shell is BN, BAs, GaN, or the like.
III-V compound semiconductor, ZnO, ZnS, ZnSe,
II-VI group compound semiconductors such as CdS, MgS, MgS
e, such as a compound of a Group 2 element of the Periodic Table and a Group 16 element of the Periodic Table, has a band gap of 2.3 eV or more at a temperature of 300 K, and is most preferably BN, BAs, or GaN. , ZnO, ZnS, ZnS
The band gap of e, MgS, MgSe or the like in a bulk state is at least 2.5 eV at a temperature of 300 K, and ZnS is most preferably used in chemical synthesis.

[Organic Ligand] The semiconductor ultrafine particles used in the present invention are mainly composed of the above-mentioned semiconductor crystal particles.
It is desirable that the semiconductor crystal particles form an ultrafine semiconductor particle by bonding an organic ligand to the surface thereof. Such an organic ligand means an organic molecule that binds to the surface of the semiconductor crystal particle in an arbitrary bonding mode (for example, a coordination bond, a covalent bond, an ionic bond, a hydrogen bond, or the like) by a coordination functional group described below. I do. As long as the object of the present invention is not significantly impaired, the chemical structure of the organic ligand is not limited, and plural kinds of organic ligands may be used in combination.

The role of the organic ligand is to control the affinity between the eccentric target phase detected by the analysis method of the present invention and the semiconductor crystal particles (hereinafter referred to as “dispersion effect”), and / or An object of the present invention is to exhibit an effect of shielding crystal particles from external influences such as the atmosphere (particularly oxygen gas and water) and holding the crystal particles (hereinafter, referred to as “shielding effect”). From the viewpoint of such a shielding effect, the organic ligand preferably has a methylene group chain having 4 or more carbon atoms. The shielding effect is
Water, methanol, ethanol, in a solution of a protic solvent such as ethylene glycol, a solution of a protic acid base such as hydrogen chloride or ammonia in the protic solvent solution, or a hydroxyl group, a thiol group, an amino group, a carboxyl group, an amide group, etc. The effect is remarkably exhibited in a phase separation system containing molecules having active hydrogen. This is because the methylene group chain forms a kind of hydrophobic barrier on the surface of the semiconductor crystal due to its hydrophobicity, and the polar chemical species such as the protic solvent molecules or protonic acid bases approach the semiconductor crystal surface to form the semiconductor crystal. It is presumed to be due to a mechanism of preventing adverse effects such as elution of the formed metal element. By using such an organic ligand having a methylene group chain having 4 or more carbon atoms, specifically, the emission characteristics of the semiconductor crystal particles are often stabilized. The number of carbon atoms in this methylene group chain is usually 4-20, preferably 5-16, most preferably 6
To about 12.

The coordinating functional group of the organic ligand is not limited as long as it has a binding ability to the surface of the semiconductor crystal, but a functional group containing a Group 15 or 16 element of the periodic table is usually used. . Specific examples thereof include a primary amino group (—NH ₂ ) and a secondary amino group (—NHR; wherein R is a hydrocarbon 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), 3
A ^primary amino group (—NR ¹ R ² ; provided that 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, a phenyl group, and the like); A nitrogen-containing functional group having a nitrogen-containing multiple bond such as a nitrile group or an isocyanate group; a nitrogen-containing functional group such as a nitrogen-containing aromatic ring such as a pyridine ring or a triazine ring; a primary phosphine group (-PH ₂ );
Tertiary phosphine group (-PHR), tertiary phosphine group (-P
R ¹ R ² ) a primary phosphine oxide group (—PH ₂ ＝
O) a secondary phosphine oxide group (-PHR = O), 3
Grade phosphine oxide groups ^{(-PR 1 R 2 = O)} , 1 phosphine selenide group (-PH ₂ = Se), ₂ phosphine selenide group (-PHR = Se), 3 phosphine selenide groups (-PR A functional group containing a Group 15 element of the periodic table, such as a phosphorus-containing functional group such as ¹ R ² = Se), a hydroxyl group (—OH),
Oxygen-containing functional groups such as methyl ether group (—OCH ₃ ), phenyl ether group (—OC ₆ H ₅ ), carboxyl group (—COOH), mercapto group (also called thiol group;
H), a sulfide bond group (or a thioether bond, -S
-), A disulfide bond (-SS-), a thioic acid group (-
COSH), a dithioic acid group (-CSSH), a xanthate group, a xanthate group, an isothiocyanate group, a thiocarbamate group, and a functional group containing an element belonging to Group 16 of the periodic table such as a thiophene ring. Is done. Of these, preferred are Group 15 elements of the periodic table such as nitrogen-containing functional groups such as pyridine rings, tertiary phosphine groups, tertiary phosphine oxide groups, and phosphorus-containing functional groups such as tertiary phosphine selenide groups. Is a functional group containing a Group 16 element of the periodic table, such as a sulfur-containing functional group such as a sulfur-containing functional group such as a mercapto group and a disulfide bond. Or a sulfur-containing functional group such as a mercapto group is more preferably used.

The content of the organic ligand in the ultrafine semiconductor particles is not limited, and the content varies depending on the molecular weight of the organic ligand. For example, an organic ligand having a molecular weight of about 500 or less is used. When the content is, the content is usually 10 to
It is preferably in the range of about 20 to 40% by weight from the viewpoint of the above effects of the organic ligand. Although the specific coordination chemical structure of an organic ligand on the surface of a semiconductor crystal represented by a nanocrystal has not been sufficiently elucidated, in the present invention, the coordination functional group exemplified above does not necessarily have the same structure. May not be held. For example, in the case of a mercapto group or a disulfide bond, a covalent bond with a metal element M (for example, zinc or cadmium in a group II-VI compound semiconductor, gallium or indium in a group III-V compound semiconductor) existing at the terminal of a semiconductor crystal is formed. In the case of a phosphine oxide group (P = O), a change to a structure in which a covalent bond with the metal element M is formed (for example, a structure of POM), etc. Is also conceivable.

Specific examples of preferably used organic ligands include trialkyl phosphine oxides such as tributyl phosphine oxide and trioctyl phosphine oxide (TOPO), and ω-mercapto alkane such as 6-mercaptohexane and 12-mercaptododecane. Kind, 2-
Examples thereof include ω-mercapto alcohols such as mercaptoethanol and 6-mercapto-n-hexanol, and organic ligands containing a polyalkylene glycol residue described below. Of these, TOPO and ω-mercapto fatty acid esters of polyalkylene glycols described below are particularly preferably used.

[Organic Ligand Containing Polyalkylene Glycol Residue] As the above-mentioned organic ligand, an organic ligand having a polyalkylene glycol residue is particularly preferably used in view of the dispersing effect. Is exemplified. Here, the polyalkylene glycol residue is a polymer residue represented by the following general formula (1).

[0036]

-(R ¹ O) _n -R ² (1) (wherein, in the general formula (1), R ¹ represents an alkylene group having 2 to 6 carbon atoms, R ² represents a hydrogen atom, and 1 to 7 carbon atoms) And n represents a natural number of 30 or less.) A specific example of R ¹ in the general formula (1) is ethylene. Group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentylene group, cyclopentylene group, n-hexylene group, cyclohexylene group, and the like. Group, an alkylene group having 2 to 4 carbon atoms such as an n-propylene group, an isopropylene group, or an n-butylene group, more preferably an alkylene group having 2 or 3 carbon atoms such as an ethylene group, an n-propylene group, or an isopropylene group. Group , Most preferably ethylene groups are used. In the general formula (1), a plurality of types of R ¹ may be mixed in one residue.
In such a case, the crystallinity of the polyalkylene glycol residue may be lowered, which is preferable. Such multiple R ¹
There is also no restriction on the copolymerization order (sequence) of.

Specific examples of the alkyl group used for R ² in the general formula (1) include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, benzyl group, etc., and are preferable in terms of hydrophilicity. Is an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group, more preferably a methyl group or an ethyl group, and most preferably a methyl group.
Specific examples of the aryl group used for R ² include a phenyl group, a toluyl group (monomethylphenyl group), a dimethylphenyl group, an ethylphenyl group, an isopropylphenyl group, a 4-tert-butylphenyl group, a pyridyl group,
Examples thereof include a monomethylpyridyl group and a dimethylpyridyl group. From the viewpoint of hydrophilicity, a phenyl group or a pyridyl group is preferably used. When hydrophilicity such as hydrogen bonding at the terminal is required, a hydrogen atom is also suitably used as R ² .

The natural number n in the general formula (1) is preferably 20 or less, more preferably 10 or less, and further preferably 5 or less. If the value of the natural number n is too large, the content of the semiconductor crystal particles cannot be sufficiently increased, and the analysis effect of the present invention may be insufficient. The preferred structure of the general formula (1) includes a triethylene glycol residue (R ¹ is an ethylene group, n = 3), and particularly preferred is a structure in which R ² is a hydrogen atom or a methyl group.

Such a polyalkylene glycol residue is
Although it is bonded to the surface of the semiconductor crystal particle by any of the above-mentioned coordination functional groups, a particularly preferred coordination functional group is a mercapto group. This is because the mercapto group has a particularly strong binding force to the transition metal element present on the semiconductor crystal surface. As a specific structure of the polyalkylene glycol having a mercapto group used as a ligand to a semiconductor crystal, a polyalkylene glycol ester of ω-mercapto fatty acid described later, which is a particularly preferable structure, and a general formula (2) )) Are also exemplified.

[0040]

## STR2 ## HS- (R ¹ O) _n -R ² (2) wherein R ¹ , R ² , and n in the general formula (2) and preferred examples thereof are all those of the general formula (1). Is the same as

[Ω-Mercapto Fatty Acid Ester of Polyalkylene Glycols] One of the most preferred structures of the organic ligand used in the present invention is the ω-mercapto fatty acid ester of polyalkylene glycols represented by the following general formula (3). And mercapto fatty acid esters.

[0042]

Embedded image HS— (CH ₂ ) _m —COO— (R ¹ O) _n —R ² (3) In the general formula (3), m represents a natural number of 20 or less, and R ¹ , R ² , and n And examples of these preferred cases are all the same as in the case of the general formula (1). Since the methylene group chain represented by-(CH ₂ ) _m- in the general formula (3) is a structural unit exhibiting the above-mentioned shielding effect, a preferable range of the value of the natural number m is as follows. It is the same as the description of the number of carbon atoms in the methylene group chain.

Accordingly, as a preferable molecular structure of the structure represented by the general formula (3), for example, 11-mercaptoundecanoic acid ester of polyethylene glycols can be mentioned, and among them, 11-mercapto of the following general formula (4) Triethylene glycol ester of undecanoic acid is an example of the most preferred organic ligand.

[0044]

Embedded image HS (CH ₂ ) ₁₀ COO (CH ₂ CH ₂ O) ₃ —R ² (4) However, in the general formula (4), R ² and preferred examples thereof are all those of the general formula (1). It is the same as in the above case, and in particular, those in which R ² is a hydrogen atom or a methyl group are optimal.

The ester represented by the general formula (3) or (4) is obtained by converting an ω-mercapto fatty acid such as 11-mercaptoundecanoic acid and an excess equivalent of a polyalkylene glycol into sulfuric acid and p-toluenesulfonic acid. A method of dehydrating esterification in the presence of an acid catalyst (heating and / or depressurization under reduced pressure as necessary to accelerate the equilibrium reaction); By subjecting to a transesterification reaction in the presence of a strong acid such as sulfuric acid or p-toluenesulfonic acid or a catalyst such as Lewis acid (accelerating the equilibrium reaction by heating or reducing the pressure if necessary) by subjecting the ω-mercapto fatty acid to a corresponding acidification Method of converting into active species such as anhydrides and acid anhydrides and then subjecting it to a condensation reaction with polyalkylene glycol in the presence of a base They synthesized from, but is simple inter alia dehydration esterification method.

[Organic ligand having a radical-reactive group bonded thereto] An organic ligand having a radical-reactive group, which will be described later, is an organic ligand which achieves the above-mentioned dispersion effect by reacting with the above-mentioned dispersed phase molecule. (Hereinafter referred to as "radical-reactive organic ligand"), which is suitably used when the phase separation system for analysis forms a polymer as a result of generating a polymer by radical polymerization. It is. That is,
For example, when a polymer produced by radical polymerization of a monomer contained in an initial state undergoes phase separation with a different component, or under special conditions in which the produced polymer is oriented as reported in JP-A-9-159819. In such a case, radical polymerization is performed, and in such a case, the semiconductor ultrafine particles having the above-mentioned radical-reactive organic ligand are copolymerized by the radical polymerization, and as a result, the polymer phase is formed by the radical polymerization. The semiconductor ultrafine particles can be effectively unevenly distributed.

The structure of the radical reactive group is not limited, and examples thereof include a carbon-carbon double bond, a carbon-carbon triple bond, and a cyclopropane ring. Radical-reactive groups suitable for the purpose of the present invention are structures having radical polymerizability, for example, a carbon-carbon double bond conjugated to a carbonyl group such as an acryloyl group, a methacryloyl group, or a crotonoyl group, a propargylcarbonyl group, and the like. A carbon-carbon triple bond conjugated to a carbonyl group of the following, a carbon-carbon double bond conjugated at both ends to two carbonyl groups such as a maleoyl residue or a fumaroyl residue, a 4-vinylbenzyl group, a 3-vinylbenzyl group, A carbon-carbon double bond conjugated to an aromatic ring such as a vinylnaphthylmethyl group or a vinylpyridylmethyl group; a carbon-carbon triple bond conjugated to an aromatic ring such as a propargylphenyl group, a propargylnaphthyl group or a propargylpyridyl group; vinyloxy Vinyl groups such as carbonyl, vinyloxy and vinylamino have electronegativity Structures attached to the high atomic, allyl groups such as allyloxy group and an arylamino group have structures attached to the highly electronegative atom. Among them, preferred from the viewpoint of radical polymerizability are a carbon-carbon double bond conjugated to a carbonyl group such as an acryloyl group and a methacryloyl group, and a carbon-carbon double bond conjugated at both ends to two carbonyl groups such as a maleoyl residue. A carbon-carbon double bond conjugated to an aromatic ring such as a heavy bond, a vinylbenzyl group, a structure in which a vinyl group such as a vinyloxycarbonyl group or a vinyloxy group is bonded to an atom having a high electronegativity, and an allyl group such as an allyloxy group. It has a structure bonded to an atom having a high electronegativity, and among them, a carbon-carbon double bond conjugated to a carbonyl group such as an acryloyl group, a methacryloyl group, and a maleoyl residue is most preferable.

Preferred examples of the above-mentioned radical-reactive organic ligand include three radical-reactive organic ligands such as tris (3-acryloyloxypropyl) phosphine oxide and tris (3-methacryloyloxypropyl) phosphine oxide. Phosphine oxides having a group, n-butyl-
Two radical reactive groups such as bis (3-acryloyloxypropyl) phosphine oxide, n-butyl-bis (3-methacryloyloxypropyl) phosphine oxide, and octyl-bis (3-methacryloyloxypropyl) phosphine oxide Phosphine oxides, di-n-butyl- (3-acryloyloxypropyl) phosphine oxide, di-n-butyl- (3-methacryloyloxypropyl) phosphine oxide, dioctyl-
A phosphine oxide having one radical reactive group such as (3-methacryloyloxypropyl) phosphine oxide, a radical reactive group such as 6-acryloyloxy-n-hexanethiol, 6-methacryloyloxy-n-hexanethiol, etc. Alkanethiols having 4-
Examples thereof include aryl thiols having a radical reactive group such as acryloyloxybenzene thiol and 4-methacryloyloxy benzene thiol. Among these, it has a radical reactive group such as tris (3-methacryloyloxypropyl) phosphine oxide, octyl-bis (3-methacryloyloxypropyl) phosphine oxide, dioctyl- (3-methacryloyloxypropyl) phosphine oxide. Phosphine oxides are particularly preferred in terms of radical polymerizability.

[Examples of Other Organic Ligands] In the present invention, preferred effects can be obtained by mainly using the above-mentioned preferred organic ligands. Organic ligands may be used at an arbitrary ratio or used in combination. (A) Sulfur-containing compound: mercaptoethane, 1-mercapto-n-propane, 1-mercapto-n-butane, 1-mercapto-n-hexane, mercaptocyclohexane, 1-mercapto-n-octane, 1-mercapto Mercaptoalkanes such as -n-decane; thiophenol derivatives such as thiophenol, 4-methylthiophenol and 4-tert-butylthiophenol; dialkyl sulfides such as diethyl sulfide, dibutyl sulfide, dihexyl sulfide, dioctyl sulfide and didecyl sulfide , Diethyl disulfide, dibutyl disulfide, dihexyl disulfide, dioctyl disulfide, dialkyl disulfides such as didecyl disulfide, dimethyl sulfoxide, diethyl sulfoxide, dibutyl Sulfoxide, dihexyl sulfoxide, dioctyl sulfoxide, dialkyl sulfoxides such as didecyl sulfoxide, thiourea, a compound having a thiocarbonyl group such as thioacetamide, sulfur-containing aromatic compounds such as thiophene, and the like. (B) Phosphorus-containing compound: trialkylphosphines such as triethylphosphine, tributylphosphine, trihexylphosphine, trioctylphosphine, and tridecylphosphine; aromatic phosphines such as triphenylphosphine and triphenylphosphine oxide; or aromatic phosphines. Oxides and the like. (C) Nitrogen-containing compounds: nitrogen-containing aromatic compounds such as pyridine and quinoline, trimethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, triphenylamine, methyldiphenylamine, diethylphenylamine, Tertiary amines such as tribenzylamine, diethylamine, dibutylamine, dihexylamine, dioctylamine, didecylamine, diphenylamine, secondary amines such as dibenzylamine, hexylamine, octylamine, decylamine, dodecylamine, hexadecylamine, Primary amines such as octadecylamine, phenylamine and benzylamine; carboxylic acid esters having an amino group such as triethyl nitrilotriacetic acid ester;

[Example of Design of Chemical Structure of Organic Ligands According to Analyzed Phase Separation System] The chemical structure of the above-mentioned organic ligands should be similar to the chemical structure of the target phase to be detected. Preferable examples of the combination of the former and the latter include hydrocarbon polymers such as polystyrene, polyethylene and polypropylene, organic polymers having an aliphatic chain terminal such as trioctylphosphine oxide (TOPO), polyhexyl acrylate and polyhexyl acrylate. Polymers having relatively high hydrophobicity such as acrylic resins having an alkoxy group having about 5 or more carbon atoms such as lauryl methacrylate, and polyethers such as triethylene glycol ester of 11-mercaptoundecanoic acid of the general formula (4) Such as a hydroxyl group at the terminal of an organic ligand having a terminal or 6-mercapto-1-hexanol; Polyalkylene glycols such as polyethylene glycol (or polyethylene oxide) and polypropylene glycol (or polypropylene oxide), and about 4 or less carbon atoms such as polymethyl methacrylate (PMMA) and polybutyl acrylate for organic ligands having a functional hydrogen functional group Acrylic resins having an alkoxy group, polycarbonates such as bisphenol A polycarbonate, aliphatic polyesters such as polycaprolactam and poly-3-hydroxybutyrate, aromatic polyesters such as polyethylene terephthalate, nylon 6 and nylon 66, etc. Polyamides, polymers having an ester group or amide group such as polyvinyl acetate or polyvinyl formamide in the side chain, phenoxy resins, linear epoxy resins, polyvinyl alcohol, etc. Polymers having hydroxyl side chains, aromatic cross-linked epoxy resins such as bisphenol type epoxy resins obtained using aromatic epoxy monomers such as bisphenol A diglycidyl ether, and aliphatic epoxy monomers such as ethylene glycol diglycidyl ether And relatively high hydrophilic polymers such as aliphatic cross-linked epoxy resins.

The above-mentioned organic ligand having a radical reactive group such as tris (3-acryloyloxypropyl) phosphine oxide bonded thereto can be used for radical polymerization of styrene resins such as polystyrene and acrylic resins such as PMMA. Highly ubiquitous selectivity can be achieved by a method of adding to the radical polymerization reaction system and copolymerizing it when detecting the ubiquitous target phase mainly composed of a polymer produced by the method (hereinafter referred to as “copolymerization ubiquity method”). Is obtained. An example of an analysis target system in which such a copolymerization uneven distribution method is preferably used is polystyrene or the like by radical polymerization of the styrene resin monomer in a homogeneous liquid phase containing a styrene resin monomer such as styrene and an acrylic resin such as PMMA. When the phase containing the styrene resin is the unevenly distributed target phase in the phase separation system for producing the styrene resin of the above, a homogeneous liquid containing an acrylic resin monomer such as methyl methacrylate (MMA) and a styrene resin such as polystyrene. When the phase containing the acrylic resin is the unevenly distributed target phase in a phase separation system in which the acrylic resin is formed by radical polymerization of the acrylic resin monomer in the phase, the styrene resin monomer and / or the acrylic resin monomer are used. Radically polymerizable monomers such as As those having excellent solubility, for example, styrene is obtained by radical polymerization of the above-mentioned radically polymerizable monomers in a uniform liquid phase containing the above-mentioned polyalkylene glycols, the above-mentioned polycarbonates, the above-mentioned aliphatic polyesters and the like. In a phase separation system in which a polymer generated by radical polymerization of a resin or an acrylic resin is generated, a phase containing a polymer generated by the radical polymerization may be an unevenly distributed target phase.

[Method of Producing Semiconductor Crystal Particles] The semiconductor crystal particles described above may be formed by any method such as the following conventional method of producing semiconductor crystals. (A) High vacuum process such as molecular beam epitaxy or CVD. Although high purity semiconductor crystal particles having a highly controlled composition can be obtained by this method, toxic gases such as phosphine and arsine may be used as raw materials, and expensive production equipment is required. There are restrictions on the above usage. (B) A method in which a raw material aqueous solution is present as reverse micelles in a non-polar organic solvent and crystals are grown in the reverse micelle phase (hereinafter referred to as “reverse micelle method”). S. Zou
Int. J. Quant. Chem. , 72, 4
39 (1999). A well-known reverse micelle stabilization technology can be used in a general-purpose reactor, and relatively inexpensive and chemically stable salts can be used as raw materials. It is a suitable method for production. However, the current technology may be inferior in light emission characteristics as compared with the hot soap method described below. (C) A method of injecting a thermally decomposable raw material into a high-temperature liquid-phase organic medium to grow crystals (hereinafter referred to as a hot soap method). E. FIG. B. Katari et al .; Phys
s. Chem. , 98, 4109-4117 (199
This is the method reported in 4). Semiconductor crystal particles having excellent particle size distribution and purity are obtained as compared with the reverse micelle method, and the product is excellent in luminescence characteristics and is usually soluble in an organic solvent. For the purpose of desirably controlling 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 coordination force for a semiconductor constituent element is used as a liquid phase component (which also serves as a solvent and a ligand). ). Examples of such coordinating organic compounds include the above-mentioned trialkylphosphines, the above-mentioned trialkylphosphine oxides, ω-aminoalkanes such as dodecylamine, tetradecylamine, hexadecylamine and octadecylamine, and the above-mentioned dialkyl Sulfoxides and the like.
Of these, trialkyl phosphine oxides such as TOPO and ω-aminoalkanes such as hexadecylamine are preferred. (D) A solution reaction involving semiconductor crystal growth similar to the above-described hot soap method, but a method of performing an acid-base reaction at a relatively low temperature as a driving force has been known for a long time (for example, PA Jackson). J. Cryst. Growth
h, 3-4, 395 (1968)).

The semiconductor raw materials usable in the liquid phase production method include a substance containing a positive element selected from Groups 2 to 15 of the periodic table and a negative element selected from Groups 15 to 17 of the periodic table. Substances. For example, in the hot soap method, organometals such as dimethylcadmium and diethylzinc, selenium alone dissolved in tertiary phosphines such as trioctylphosphine and tributylphosphine, and chalcogenide elements such as bis (trimethylsilyl) sulfide are used. A method of reacting the compound with TOPO is preferably used. Further, when, for example, zinc oxide is produced by the solution reaction of the above (d), L.I. Spanh
el et al; Am. Chem. Soc. , 113, 2
The method of reacting zinc acetate and lithium hydroxide in ethanol described in page 826 (1991) is preferably used. When there are a plurality of types of semiconductor raw materials, these may be mixed in advance, or may be individually injected into the reaction liquid phase. These raw materials may be used as a solution using an appropriate diluting solvent.

The method for bonding the organic ligand to the semiconductor crystal particles is not limited, but preferred methods include direct introduction of the coordinating organic compound by the hot soap method, or A ligand exchange reaction by an organic ligand having a strong coordination force having a mercapto group is exemplified. [Confocal microscope] The confocal microscope according to the present invention is a microscope having a mechanism schematically shown in FIG. That is, the light beam (dashed line; the arrow indicates the traveling direction of the light) emitted from the light source a is condensed by the condenser lens b and then by the incident light slit c.
Is reflected by a beam splitter (beam separator) d, and a focal point f (a horizontal solid line in the sample A) is focused in the sample A of the phase separation system by the objective lens e. The light emitted from the focal plane f (broken line) passes through the objective lens e and then passes through the beam splitter d, passes through a confocal slit g controlled at the focal point, and is observed. Light emitted from a plane other than the focal plane is not focused at the confocal slit g and cannot pass through the confocal slit g and is not observed.

Therefore, by scanning the focal plane (scanning) and moving the confocal slit in conjunction with the scanning, it is possible to observe images on a plurality of planes in the depth direction of the sample. Images can be combined. [Phase Separation Structure Analyzing Apparatus] The phase separation structure analyzing apparatus of the present invention is a confocal microscope equipped with a transparent container (corresponding to a in FIG. 1) mainly used for observation of a liquid phase sample. It is. Such a transparent container is particularly useful as a sample container when analyzing a phase separation process in a liquid phase.

The material of the transparent container has a practically acceptable light transmittance at the wavelength of the incident light or the light emission (broken line in FIG. 1) and a practically acceptable light transmittance for the liquid phase sample. There is no limitation as long as it has chemical resistance. For example, BK7 (borosilicate crown glass), silica glass (or quartz glass) such as optical grade fused silica or UV grade fused silica, optical crown glass, LEBG (low Expanded borosilicate glass), sapphire, zinc selenide, LaSFN9, SF11, F
2. Amorphous inorganic glass materials such as BaK1, quartz, etc., acrylic resins such as polymethyl methacrylate (PMMA), styrene resins such as polystyrene, and aromatic polycarbonate resins such as bisphenol A polycarbonate A synthetic resin material, a synthetic resin material having excellent chemical resistance such as Teflon (registered trademark), polyethylene, and polypropylene, or an elastomer such as silicone rubber is used.

The shape and dimensions of the transparent container are not particularly limited as long as the analysis intended in the present invention is not made extremely difficult. Are preferred. The upper wall (ceiling of the container) through which the incident light and the luminescence pass is not necessarily required because the purpose of the transparent container is to prevent the liquid sample from diffusing and flowing away and to stably face the objective lens. However, it is desirable to provide the upper wall for the purpose of reducing the odor and the uncontrollability of the stoichiometry accompanying the evaporation and boiling of the components of the liquid phase sample. In order to minimize the influence of the upper wall on optical observation as much as possible, its thickness is desirably as small as possible in principle. However, in terms of mechanical strength, the thickness is usually 0.1 to 10 mm, preferably Is 0.5 ~
The range is about 5 mm.

The transparent container described above is used for controlling the influence of the temperature on the phase separation behavior of the sample a in FIG.
It is preferable to be in contact with the temperature control mechanism c. Such a temperature control mechanism may use any heating or cooling device (for example, an electric heating device such as a casting heater or a ribbon heater, and / or a cooler having a mechanism for flowing a refrigerant), and the sample may be used as necessary. A thermocouple for measuring the internal temperature may be installed inside the transparent container, and the temperature may be controlled precisely and automatically by a temperature controller. In addition, the heating controlled by the temperature control mechanism activates a thermally decomposable reaction initiator present in the liquid phase sample, that is, a compound which generates an active chemical species such as a radical, an acid or a base by thermal decomposition. Or the intention of removing volatile components by evaporation or boiling as described later.

The transparent container described above may have a degassing mechanism schematically shown by f in FIG. The degassing mechanism is provided for the purpose of discharging gas generated inside the transparent container to prevent an undesired increase in the internal pressure of the container, and / or by actively removing gas components generated by a chemical reaction of the sample. It may be preferable for the purpose of reaction control such as promotion of the chemical reaction. Examples of such a chemical reaction include a case where a polymer generated by condensation polymerization of, for example, polyester, polycarbonate, or polyamide is formed in a liquid phase sample. In such condensation polymerization, water, methanol, ethanol, phenol, and the like are usually used. Since the reaction equilibrium shifts to the polymer generation side due to the elimination of volatile low-molecules and the active removal thereof, it may be preferable to provide the degassing mechanism. The degassing mechanism is suitably used not only for such a chemical reaction, but also for performing evaporation or boiling for the purpose of removing the solvent from the liquid phase sample and removing the distilled solvent vapor. Therefore, for the purpose of arbitrarily adjusting the internal pressure of the transparent container, the degassing mechanism may be released to the atmosphere, or may be connected to an exhaust device such as a vacuum pump via a pressure reduction degree adjusting valve, Alternatively, it may be connected to a pressure valve that adjusts to a desired degree of pressurization,
A cooler for condensing and recovering the outflowing gas may be connected to the end.

The transparent container may be fixed to the apparatus at all times and intended for repeated use by cleaning the inside, or may be designed to be easily detachable and replaceable. Further, the upper wall may be designed to be detachable. The phase separation structure analyzing apparatus of the present invention may have a light irradiation mechanism for activating a photoreaction initiator in a liquid phase sample in the vicinity of the transparent container. By mounting such a light irradiation mechanism, a photoreaction initiator, that is, a chemical reaction initiated by the activation of a compound generated by a decomposition reaction by light irradiation of an active chemical species such as a radical, an acid, or a base in the liquid phase sample. It is possible to proceed. At this time, the above-mentioned temperature control mechanism and gas release mechanism may be used together.

As the light irradiation mechanism, a mercury lamp,
Any light source that emits light of the wavelength required for the desired photoreaction, such as a light source in the ultraviolet to visible wavelength range, such as a xenon lamp, or a light source in the mainly visible wavelength range, such as an incandescent lamp or a fluorescent lamp, is used. Is done. Although the output of such a light source is not limited, in practice, the output of the light source is usually 1 to 500 watts /
cm ² , preferably about 10 to 200 watts / cm ² . The distance between the light irradiation mechanism and the transparent container is not limited, and is adjusted by the output of the light source. The light intensity on the sample surface is usually 0.1 to 100 milliwatts / c.
m ² , preferably about 1 to 50 milliwatts / cm ² , it is desirable to design the apparatus so that the distance is variable.

[0062]

The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. [Apparatus and Conditions] (1) Light source used for photocuring reaction: Metal halide lamp M01L21 (length 1) manufactured by LAN Technical Service
25 mm, output 80 watts / cm ² , emission wavelength distribution is 2
20 to 700 nm, and has a maximum energy distribution around 360 to 390 nm). (2) Confocal microscope: Leica TCS NT type confocal laser scanning microscope was used. The microscope used was an inverted microscope at infinity optics. The light source used is described in each example described later. To observe the image, the linear beam formed on the focal plane by the incident light slit is converted to the focal plane (X-
One image data was obtained by scanning on the (Y plane), and this scanning was performed at a constant speed in the z-axis direction (depth direction) as necessary. Synthesis Example 1 Synthesis of Ultra Fine CdSe Fine Particles by Hot Soap Method (1) Preparation of Raw Material Liquid At room temperature, 90% pure trioctylphosphine oxide supplied from Aldrich in the air (350 g,
(Hereinafter abbreviated as TOPO) in a 500 mL screw-bottle bottle, covered with a dry argon gas line and a lid provided with a gas vent, passed an argon gas stream for 1 hour, and the inside was replaced with an argon atmosphere. Heated and melted in an oil bath at ℃.

On the other hand, in a glove box kept at room temperature in a dry nitrogen atmosphere, selenium (simple) powder (1.20) having a purity of 99.999% supplied from Aldrich was supplied.
g) into another 500 mL screw cap bottle,
Tri-n-butylphosphine (52.05 g) having a purity of 99% supplied from m Chemicals was added, and the mixture was stirred with a magnetic stirrer for 10 minutes. As a result, selenium was dissolved while generating heat to give a transparent solution. In the glove box, here is also the Strem Chemi
hexane diluent of 99 +% dimethyl cadmium supplied by Cals Inc. (dimethyl cadmium concentration is 1
0% by weight; 26.17 g as a solution) was added and stirring was continued for 3 minutes to obtain a clear solution. (2) Production of CdSe Ultrafine Particles The horizontal flow method synthesis apparatus schematically shown in FIG. 2 was used. The raw material liquid was charged in the storage tank 4 and TOPO was charged in the medium storage tank 1. However, the medium storage tank 1 was kept at a temperature higher than the melting point of TOPO. The temperature settings of the temperature control portions corresponding to the medium pre-heating device 3, the raw material supply system pre-temperature control device 6, the reaction heating device 8, and the aging heating device 10, respectively, are set at 350 ° C., 20 ° C., 350 ° C., and 300 ° C. And The region where the temperature was controlled was up to 6.7 seconds before the semiconductor raw material 4 was injected into the reactor 7. The temperature of the circulating high-temperature water tank 11 at the outlet of the reaction solution was set at 60 ° C. The medium feed pump 2 is 10.6 mL / min, and the raw material feed pump 5 is 3.7 m / min.
Each of them was driven with the capacity of L, and liquid feeding was started. At the point 9 inside the reactor 7 in FIG. 2, the medium (TOPO) and the raw material liquid merged, and the Reynolds number Re at this point was 1,900. A red reaction mixture containing CdSe ultrafine particles was used as a glass material 1000 corresponding to the product storage 12.
Collected in mL screw cap bottle. (3) Purification of CdSe ultrafine particles In order to purify the obtained CdSe ultrafine particles, the contents in a glass-made 1000 mL screw-cap bottle corresponding to the above-mentioned product storage 12 were collected, and were collected here by Wako Pure Chemical Industries. Was added and stirred, and a suspension containing a red precipitate was obtained. Add all of this suspension to 3
After centrifugation at 000 rpm for 15 minutes, the supernatant was discarded, the remaining precipitate was blown with dry nitrogen gas, pre-dried, and then vacuum-dried at room temperature for 15 hours to obtain purified Cd.
Se ultrafine particles were obtained. The number average particle diameter of the CdSe nanoparticles, Hitachi Co., Ltd., about was observed by H-9000UHR transmission electron microscope (accelerating voltage 300 kV, vacuum of about 7.6 × 10 over ⁹ Torr at the time of observation) 4 nm with a standard deviation of about 20%. The CdSe ultrafine particles emitted red light at an excitation wavelength of 488 nm.

Example 1 Analysis of Phase Separation Structure of Photocurable Resin by Addition of Ultrafine CdSe Fine Particles A bifunctional methacrylate type monomer of the following formula (5) (hereinafter simply referred to as “bifunctional monomer”) and cyanoethyl methacrylate were combined with one another. : 1 in a weight ratio of 0.1: 1 in this total amount.
2,4,6-trimethylbenzoyldiphenylphosphine oxide (hereinafter abbreviated as TBDP) in an amount of 1% by weight
Was added as a photoradical initiator under light-shielding conditions, and dissolved by stirring at room temperature for 5 minutes. This is hereinafter referred to as “monomer mixture”. Note that TBDP decomposes upon irradiation with light in a wavelength region of 420 nm or less to generate radicals. The Cd obtained in Synthesis Example 1 was mixed with this monomer mixture.
A solution of Se ultrafine particles in toluene was added to a concentration of 0.5% by weight. However, the concentration of the added ultrafine CdSe particles was adjusted so as to be 0.001% by weight of the monomer mixture. This is hereinafter referred to as “curing raw material liquid A”.

[0065]

Embedded image

The curing raw material liquid A was injected between two glass plates sandwiching a circular rubber packing having an inner diameter of 75 mm (a gap between the glass plates was 2 mm), and the light intensity on the surface of the sample was 7.2. The metal halide lamp was placed parallel to the sample surface at a distance of milliwatts / cm ^2, and light irradiation was performed for 150 seconds in a room temperature atmosphere. This light source is the TB
It contains light having a wavelength at which DP is decomposed to effectively generate radicals. Light As a result, a plate-shaped molded body of a photocurable resin composition in which ultrafine CdSe particles were dispersed was obtained.
Observation was performed using the confocal microscope described above. The light source used was 488 nm wavelength light of an argon / krypton laser (output: 75 milliwatts), and the objective lens used had a magnification of 10 times. At this time, the scanning speed of the scanning unit is set to the maximum (2048 × 2048 pixels).
The -Y plane resolution was 0.18 μm (half width), and the Z-axis direction resolution was 0.35 μm (half width). As a result, light emission of the CdSe ultrafine particles unevenly distributed in a stripe shape was observed as shown in the photograph of FIG. However, in FIG. 3, the coordinate axes in the photograph 1 represent the x-axis and the y-axis in this observation, the scale represents 100 μm on the photograph, and the xy plane is taken from the sample surface, ie, the metal halide lamp irradiation surface in Synthesis Example 2. Represents the observed image of Also, since the z-axis stands in the vertical direction from the paper of Photo 1, Photo 2 shows an observation image from the xz plane, and Photo 3 shows an observation image from the xz plane.

Reference Example 1: Photocurable resin without addition of ultrafine CdSe particles In Example 1, the same operation was carried out by adding the same weight% of toluene instead of the toluene solution of ultrafine CdSe particles, and the same operation was carried out. A plate-like molded body was obtained. Such a molded product corresponds to a photocurable resin molded product having a molecular orientation structure disclosed in Japanese Patent Application Laid-Open No. 9-159819, and FIG. 3 shows the light emission of the CdSe ultrafine particles observed in Example 1 above.
It was observed by an optical microscope that an oriented phase-separated structure having the same interval (several μm) as in Photo 1 was provided. Such an orientation phase separation structure is understood as a phase separation structure between a molecular orientation phase (which is considered to be a kind of crystal phase due to dense orientation of polymer chains) and a non-orientation phase. The uneven distribution of the CdSe ultrafine particles of Example 1 is as follows.
It is considered that CdSe ultrafine particles remain and concentrate in such a non-oriented phase.

Comparative Example 1: Observation of transmitted light of photocurable resin to which CdSe ultrafine particles were added The transmitted light image (image based on the same principle as that of ordinary optical microscope observation) simultaneously obtained by the confocal microscope observation in Example 1 was used. No streak-like structure shown in Photo 1 of FIG. 3 was observed. That is, in the conventional optical microscope observation, the phase separation structure analysis that was possible in Example 1 is impossible.

Example 2 Analysis of Phase Separation Process of Photocurable Resin The curing raw material liquid A of Example 1 was covered with a slide glass and a cover using a silicone rubber packing having an inner wall dimension of 1 cm square and a thickness of 1.5 mm. It was sealed between glasses and placed on the sample stage of the confocal microscope. C as light source
An argon laser manufactured by Oherent (output: 600 mW, wavelength: 350 nm) was used. This wavelength is within a wavelength range in which the TBDP dissolved in the curing raw material liquid A is decomposed to effectively generate radicals. The objective lens had a magnification of 100 times, and the linear beam of the light source was scanned at a rate of 0.8 sec / scan in the same xy plane without moving the focal plane in the z-axis direction. ,
The luminescence image data of the CdSe ultrafine particles by this beam excitation was collected. FIG. 4 shows a change in the light emission image with the passage of time when the scan start time is set to 0 second. That is, FIG. 4A shows an image after 0.8 seconds (first scan), and FIG. 4B shows an image after 128 seconds (160th scan). In each photograph, the scale indicated by a white line indicates 20 μm, and a clear light emitting point considered to be due to aggregation of the ultrafine CdSe fine particles is indicated by a white arrow. It can be seen that as the photocuring reaction progresses, the number of light emitting points in the image of the CdSe ultrafine particle aggregate increased. This is because the solubility of the ultrafine CdSe particles is decreased due to the progress of the photocuring reaction (that is, the molecular weight is increased), the number of the aggregates is increased, or the size of the existing aggregates is increased, and the aggregates are detected. It was interpreted as having been done. The reason why a considerable number of CdSe ultrafine particles have already been aggregated in the first scan and the position is not retained in the photograph (b) is that the solubility of the CdSe ultrafine particles is not already sufficiently large in the initial solution. Therefore, there are some aggregates that cannot be completely dissolved from the beginning, and since the curing raw material liquid A has sufficient fluidity at the very beginning of light irradiation, the position of the aggregates from the beginning is Is interpreted to be due to the movement accompanying the mass transfer in the photocuring process.

Example 3 Analysis of Phase Separation Structure between Light-Irradiated and Non-Light-Irradiated Parts of Photocurable Resin In preparing the curing raw material liquid A of Example 1, CdSe was used.
A curing raw material liquid B was obtained by performing the same preparation operation except that the concentration of the ultrafine particles was adjusted to 1/10, that is, 0.0001% by weight of the monomer mixture of Example 1. This hardening raw material liquid B was set on a sample stage of a confocal microscope so as to be in the same state as in Example 2. The light source was also the same laser of 350 nm wavelength as in Example 2, the focal plane depth was about 50 μm from the surface, and a 1 mm square area of the sample surface was scanned 120 times (ie, a total of 96 seconds) at the same scanning speed as in Example 2. An operation was performed to perform a photocuring reaction. After stopping the scanning, the sample stage is moved 0.5 m in the positive direction of the y-axis.
m. Then, in order to observe a 1 mm square area including the lower half of the continuous irradiation area and the area of the same area as the lower half which is considered to be a non-light irradiation area, the light source was replaced with the light source used in Example 1. Using the light having the wavelength of 488 nm, the z-axis direction was scanned over a depth of 142.5 nm under the same conditions as in Example 1 to obtain a three-dimensional image. However, only the scan pitch in the z-axis direction was changed to 2.5 nm. In addition, 4
Since 88 nm is a wavelength that does not decompose the above-mentioned TBDP, which is a photoradical initiator, it was considered that a new photocuring reaction would not occur in a non-light irradiation region due to light of this wavelength.

This image is shown in FIG. However, the scale shown by the white line in FIG. 5 is 100 μm, the white line drawn in a rectangular parallelepiped is the shape of the entire sample, and the white broken line is the continuous irradiation area (A in FIG. 5) and the non-light irradiation area (FIG. B and C in 5)
, Respectively, represents the boundary. Further, as shown by the white broken arc in FIG. 5, two more types of regions (B and C in FIG. 5) were clearly identified in the non-light-irradiated regions. That is, by the operation of the present embodiment, 3 shown by A, B, and C in FIG.
Two different state regions were identified.

In FIG. 5, the reason that the continuous irradiation area A emits light brighter than the non-light irradiation area B is that a large amount of aggregates of CdSe ultrafine particles are generated as a result of the progress of the photocuring reaction in the area A. Was considered one. on the other hand,
The generation mechanism of the two types of areas B and C in the non-light irradiation area is not known at present, but the following mechanism is assumed, for example. In other words, it is presumed that the radical polymerization reaction in the region A spreads to the adjacent region B to some extent, so that a certain amount of high molecular weight occurs, and also a certain amount of aggregates of ultrafine CdSe particles are generated in the region B.

Therefore, it is presumed that the region C shows a liquid phase in which the photocuring hardly progressed, and in this region, several short linear trajectories along the broken line arc were actually formed by the operation of this embodiment. Can be seen. That is, this can be interpreted as a trajectory of light emission of aggregates of CdSe ultrafine particles reflecting the mass transfer in the liquid phase accompanying the photocuring reaction. In addition, assuming such a mechanism, the fact that the boundary between the regions B and C is not a straight line but an arc shape means that the dynamic range of the mass transfer and radical polymerization reaction in such a stationary photocuring system should be considered. The present invention provides novel knowledge not described above, and strongly supports the usefulness of the method and apparatus for analyzing a phase separation structure of the present invention.

[0074]

The method and apparatus for analyzing the phase separation structure of the present invention detect the strong luminescence of semiconductor ultrafine particles unevenly distributed in a specific phase in a phase separation system containing a polymer by a confocal microscope, and determine the distribution thereof. This makes it visible as a three-dimensional image. Therefore, a new multiphase material requiring a high degree of control of the fine phase separation structure, for example, an industrial application in which it is necessary to track the phase separation process in the liquid phase during the polymer formation process of the polymerizable monomer, for example, such a process It is used for the production process management etc. of the new multi-phase material manufactured by the company.

[Brief description of the drawings]

FIG. 1 is a configuration diagram illustrating an example of a confocal microscope.

FIG. 2 is a configuration diagram of a horizontal flow method synthesis apparatus used in an example.

FIG. 3 is a photograph observed with a confocal microscope in Example 1.

FIG. 4 is a photograph observed with a confocal microscope in Example 2.

FIG. 5 is a photograph observed with a confocal microscope in Example 3.

[Explanation of symbols]

 a Light source b Condensing lens c Incident light slit d Beam splitter (beam splitter) e Objective lens f Focal plane g Confocal slit a Phase-separated sample i Transparent container c Temperature control mechanism d Thermocouple e Temperature controller f Gas release Mechanism 1 Medium storage tank 2 Medium liquid sending pump 3 Medium preheating device 4 Semiconductor raw material storage tank 5 Raw material liquid feeding pump 6 Raw material supply system preliminary temperature control device 7 Reactor 8 Reaction heating device 10 Aging heating device 11 Circulating high temperature water tank 12 Product storage tank

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Watanabe 8-3-1 Chuo, Ami-machi, Inashiki-gun, Ibaraki Prefecture Inside the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Yukio Yamaguchi 574 Ozenji Temple, Aso-ku, Kawasaki-shi, Kanagawa Prefecture −14 (72) Inventor Shinya Maenozono 5-21-18, Nara, Aoba-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Takashi Uematsu 1-8-37 Heiwadai, Nagareyama-shi, Chiba F-term (reference) 2G043 AA03 BA14 CA04 DA02 EA01 FA02 GA02 GA07 GB19 GB21 HA01 HA09 KA09 LA01 LA03 2G059 AA05 BB16 GG00 HH02 HH03 HH06 JJ11 JJ22 KK07 2H052 AA08 AD23 AD24 AD25 AE13

Claims (7)

[Claims] Claims: 1. Ultra-fine semiconductor particles having enhanced compatibility with a specific phase in a phase separation system are allowed to coexist in the phase separation system,
A method for analyzing a phase separation structure, comprising detecting the semiconductor ultrafine particles with a confocal microscope. 2. The phase separation system to be analyzed is a phase separation process of a polymer, wherein the semiconductor ultrafine particles have an organic ligand bonded thereto, and the organic ligand has a higher phase to a specific phase. The method for analyzing a phase separation structure according to claim 1, wherein the semiconductor ultrafine particles are unevenly distributed due to compatibility. 3. The method of analyzing a phase separation structure according to claim 2, wherein the step of polymer phase separation is either a step of forming a polymer by a polymerization reaction or a step of concentrating a solution containing the polymer. 4. The method for analyzing a phase separation structure according to claim 1, wherein the emission of the semiconductor ultrafine particles is observed. 5. An apparatus for analyzing a phase separation structure, wherein a confocal microscope is provided with a transparent container used for observation of a liquid phase sample. 6. The phase separation structure analyzing apparatus according to claim 5, wherein the transparent container is in contact with the temperature control mechanism. 7. The phase separation structure analyzing apparatus according to claim 5, wherein the transparent container has a degassing mechanism.