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Polymer Particles And Use Thereof

Abstract: The present invention provides polymer particles which contain the components (a) and (b) described below and have a volume average particle diameter (D50) of from 1 nm to 1 000 nm (inclusive). (a) an amphiphilic polymer (b) a compound the fluorescence characteristics or the light absorption characteristics of which change in response to a change of a specific environmental factor

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Patent Information

Application #
Filing Date
19 December 2014
Publication Number
16/2016
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
Parent Application

Applicants

MITSUI CHEMICALS INC.
5 2 Higashi Shimbashi 1 chome Minato ku Tokyo 1057117

Inventors

1. NAKAYAMA Norio
c/o Mitsui Chemicals Singapore R&D Centre Pte. Ltd. 50 Science Park Road #06 08 The Kendall Singapore Science Park II Singapore 117406
2. MAKIO Haruyuki
c/o Mitsui Chemicals Singapore R&D Centre Pte. Ltd. 50 Science Park Road #06 08 The Kendall Singapore Science Park II Singapore 117406
3. TAKAHASHI Katsuyuki
c/o Mitsui Chemicals Singapore R&D Centre Pte. Ltd. 50 Science Park Road #06 08 The Kendall Singapore Science Park II Singapore 117406

Specification

SPECIFICATION
POLYMER PARTICLES AND USE THEREOF
5 TECHNICAL FIELD [0001]
The present invention relates to polymer particles, and an aqueous dispersion, a mixed composition, or an organic/inorganic composite thereof; and a sensor, a component for detecting a
10 temperature, an oxygen concentration, or an ion concentration, a component for a photochromic lens, and a component for a chromic window, including the same. More specif leal],y, the present invention relates to a fluorescent dye, polymer particles for immobilizing a chromic material and a method for immobilizing the polymer particles, an
15 optical fiber type temperature detecting element, a temperature
sensitive paint, a temperature sensitive film, a probe for measuring an intracellular temperature (a fluorescent probe for bio-imaging), various types of sensors (for pressure, oxygen, metals, pH, or the like), a chromic film, a chromic coating agent, or a chromic window.
20 BACKGROUND ART [0002]
Recently, various fluorescent materials (fluorescent dyes, fluorescent protein, or the like) that exhibit a change in fluorescent characteristics {fluorescent spectra and the like) in response to
25 a change in a specific environmental factor have been developed and have been investigated for their applications in various fields. A technique for measuring the temperature of a microscopic region in

2
a micro-size through molecular size scale by employing the temperature sensitivity of a fluorescent material with high accuracy has been investigated (Patent Document 1). [0003] 5 A fluorescent type optical fiber thermometer is used to measure a temperature in response to a change in a fluorescence intensity emitted from a fluorescent material due to a change in the temperature by using an optical fiber having a temperature-sensitive fluorescent material placed at the tip, and its applications in various fields
10 such as semiconductors, food, or medical fields can be expected. Further, in Fluorescent Microthermographic Imaging (FMl) for measuring a temperature using a Thermal Sensitive Paint {TSP} or a fi],m having the temperature sensitive paint coated thereon, irradiation of a subject with excitation light makes a dye emit light,
15 the light-emission intensity is correlated with temperature, and the intensity distribution is measured by means of a CCD camera to determine the surface temperature range of a microscopic region. Applications in a semiconductor field, an aviation field, a marine field, an automobile field, a medical field, or the like are expected
20 (Patent Document 2). [0004]
Similarly, chromic materials (photochromic materials, thermochromic materials, or the like) that exhibit a change in light absorption characteristics (absorption spectra or the like) in
25 response to a change in a specific environmental factor have been developed, and are applied in spectacle lenses, light modulating materials, display materials, ink materials, optical recording

3
materials, optical switches, sensor materials, or the like (Patent Documents 3 and 4). RELATED DOCUMEMT PATENT DOCUMENT 5 [0005]
[Patent Document 1] Japanese Laid-open Patent Publication No. 1997-178575
[Patent Document 2] Japanese Laid-open Patent Publication No. 2001-4460 10 [Patent Document 3] Japanese Translation of PCT International Application Publication No. 1999-511765
[Patent Document 4] Japanese Translation of PCT International Application Publication No. 2003-502693
15 SUMMARY OF THE INVENTION
PROBLEM TO BE SOLVED BY THE INVENTION [0006]
However, a temperature detection unit in a measurement tool utilizing fluorescent characteristics is generally composed of a
20 temperature-sensitive fluorescent material responsible for light emission and a polymer that is a binder. For its immobilization, a mixed composition dissolved in a solvent is directly coated on a tip of fibers, a film surface, or a subject. The solvent in the temperature-sensitive paint coated is volatilized immediately, and
25 only the polymer and the fluorescent material remain to form a thin film. At this time, the location-dependency of the volatile state is affected, depending on the solvent, and thus, portions where only

4
much fluorescent material aggregates are generated. Thus, a thin film having non-uniform dispersion characteristics of the fluorescent material may be formed J.n some cases. This phenomenon aifects the measurement accuracy by causing imbalance in light 5 emission intensity for the same temperature. In particular, in the measurement at a microscopic region, the effect is remarkably shown. Further, detachment of the fluorescent materials or the like during use is a concern in the case where adhesion of a binder to a subject is not sufficient. Furthermore, recently, with the development of
10 various bio~imaging techniques, probes for measuring a temperature J.n cells or probes for measuring various metals {bio-imaging fluorescent probes) have been investigated. However, among these probes, there are some probes that cannot maintain stability j.n an aqueous environment and are prevented from being developed as a
15 bio-imaging fluorescent probe. [0007]
Thus, temperature measurement techniques and bio-imaging using fluorescent materials have been studied extensively, but materials satisfying sufficient performance, repeat resistance, and stability
20 in an aqueous environment have not still been found. [0008]
In addition, a chromic material utilizing light absorption characteristics is generally composed of a chromic material and a resin that is a binder. The chromic dye is cured after being mixed
25 with an oligomer. Alternatively it is mixed into a polymer solution dissolved in a solvent, directly coated onto a film surface or a subject, and only the polymer and the fluorescent material remain

5
after volatilization of the solvent, thereby forming a thin film. The absorption characteristics of the chromic materials generally change due to a reversible change in the chemical structure depending on a change in the environment such as in light and heat. At this 5 time, a sufficient reversible change may not occur due to a significant reduction in the change in the chemical structure due to an effect from the polymer that is a binder nearby. [0009]
As described above, a practical use in lens materials, light
10 modulating materials, and display materials, using chromic materials, has been initiated, but sufficient performance has still not been obtained at present, [0010]
It is an object of the present invention to provide a sensor
15 that can detect a change in environment such as temperature with high accuracy, is excellent in repeated use, and can be used stably even in an aqueous environment; po],ymer particles to be used to obtain such a sensor; and polymer particles to be used to obtain a chromic material that can respond to a change in environment such as light
20 and heat with high accuracy and is excellent in repeated use. SOLUTION TO PROBLEM [0011]
That is, the present invention includes the following inventions.
25 (1) Polymer particles comprising the following components (a) and (b) and having an- average particle diameter of 50% by volume of equal to or more than 1 nm and equal to or less than 1000 nm:

(a) an amphiphilic polymer; and
(b) a compound exhibiting a change in fluorescence characteristics or light absorption characteristics in response to a change in a specific environmental factor.
5 [0012]
(2) Polymer particles comprising the following components (a) and (b) and having an average particle diameter of 50% by volume of equal to or more than 1 nm and equal to or less than 1000 nm: (a) an amphiphilic polymer; and 10 (b) a compound exhibiting a change in fluorescence
characteristics in response to a change in a specific environmental
factor,
[0013]
(3} The polymer particles as described in (1) or (2), in which 15 (a) is a polymer particle represented by the following general formula (1) and is a terminally branched copolymer having a number average molecular weight of equal to or less than 2.5 x 10^,
-c—cH—:
wherein, in the formula (1), A represents a polyolefin chain; 20 R' and R"^ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R' and R'^ is a hydrogen atom; and X^ and X'^ are the same as or different from each other and each represent a group containing a linear or branched polyalkylene glycol group,

7
[0014]
(4) The polymer particles as described in (3) , in which in the
terminally branched copolymer represented by the general formula (1) ,
X"'" and X^ are the same as or different from each other, and are each
5 a group represented by either of the genera], formulae (2) and (4),
E—X3 (2)
wherein, in the formula (2), E represents an oxygen atom or a sulfur atom; and X^ represents a polyalkylene glycol group or a group represented by the general formula (3),
.3_„
m (3)
10
wherein, in the formula (3), R represents an (m+l)-valent hydrocarbon group; Gs are the same as or different from each other and each represent a group represented by -OX^ or -NX^X^ (X^ to X^ each represent a polyalkylene glycol group); and m is the bonding number 15 for R^ to group G, and represents an integer of 1 to 10,
—N-X7 ,^,
wherein, in the formula (4) , X^ and X^ are the same as or different from each other.and each represent a polyalkylene glycol group or a group represented by the general formula (3). 20 [0015]
(5) The polymer particles as described in (4), in which the terminally branched copolymer is represented by the following general formula (la) or (lb),


Oi-H
m

(la)

wherein, in the formula (la) , R^ and R^ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R'' and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R' is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R^ is a hydrogen atom; 1 + m represents an integer of equal to or more than 2 and equal to or less than 450; andn represents an j.nteger of equal to or more than 20 and equal to or less than 300,
~"oA-H
10 ^1*^^
wherein, in the formula (lb) , R^ and R^ each represent a hydrogen
atom or an alkyl group having 1 to 18 carbon atoms, and at least one
of R^ and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen
atom or a methyl group, and at least one of R^ and R^ is a hydrogen
15 atom; R^ and R^ each represent a hydrogen atom or a methyl group, and
at least one of R^ and R^ is a hydrogen atom; R^'^ and R^"'" each represent
a hydrogen atom or a methyl group, and at least one of R^° and R^"^ is
hydrogen atom; 1 + m + o represents an integer of equal to or more

than 3 and equal to or less than 450; and n represents an integer of equal to or more than 20 and equal to or less than 300. [0016]
(6) The polymer particles as described in any one of (1) to (5} ,
5 in which the average particle diameter of 50% by volume is equal to
or more than 1 nm and equal to or less than 30 nm.
(7) The polymer particles as described in any one of (1) to (6) ,
in which (b) is a temperature-sensi.tive fluorescent dye.
(8) The polymer particles as described in (7), further
10 comprising
a non-temperature-sensitive fluorescent dye as a reference for the temperature-sensitive fluorescent dye.
(9) The polymer particJ.es as described in (7) or (8), in which
the temperature-sensitive fluorescent dye is seJ.ected from a complex
15 compound of a rare earth element selected from europium (Eu), lanthanum (La), samarium (Sm), gadolinium (Gd), terbium (Tb), dysprosium (Dy) , thulium (Tm) , ytterbium (Yb) , and lutetium (Lu) with p-diketone chelating compounds, or a complex compound of iridium (Ir) with aromatic compounds. 20 (10) The polymer particles as described in (9), in which the temperature-sensitive fluorescent dye is
tris(thenoyltrifluoroacetonate)europium (III) (Eu (III)(TTA)u) or a derivative thereof.
(11) The polymer particles as described in any one of (1) to 25 (8), in which
(b) is fJ.uorescent protein. [0017]

10
(12) The polymer particles as described in any one of (1) to
(6), in which (b) is an oxygen-sensitive fluorescent dye or a
pH-sensitive fluorescent dye.
(13) The polymer particles as described in (12), in which the
5 oxygen-sensitive fluorescent dye is
tris (2-phenylpyr.i.dine) iridiuTn(III) (Ir(III) (ppy)3) or a derivative thereof, and the pH-sensitive fluorescent dye is pyranine. [0018]
(14) The polymer particles as described in any one of (1) to
10 (6), in which (b) is a chromic material.
(15) The polymer particles as described in (14), in which the chromic material is a photochromic dye.
(16) The polymer particles as described in (15), in which the photochromic dye is a naphthopyran derivative.
15 [0019]
(17) An aqueous dispersion having the polymer particles as
described in any one of (1} to (16) dispersed in water and/or a solvent
which dissolves a part of water or dissolves all of water in an
arbitrary ratio.
20 [0020]
(18) A mixed composition comprising the following (A) , (B) , and
(C), and if necessary, (D):
(A) the polymer particles as described in any one of (1) to (16) ;
(B) a metal al}<;oxide and/or a partial hydrolysis condensate
25 thereof;
(C) water and/or a solvent which dissolves a part of water or
dissolves all of water in an arbitrary ratio; and

11
(D) a catalyst for a sol-gel reaction. [0021]
(19) An organic/inorganic composite comprising the polymer particles as described in any one of (1) to (16) and a metal oxj.de. 5 (20) A sensor comprising any of the polymer particles as described in any one of (1) to (16), the aqueous dispersion as described in (17), the mixed composition as described in (18), and the organic/inorganic composite as described in (19).
(21) A temperature detecting component comprising the polymer
10 particles as described in any one of (7) to (10).
(22) An oxygen detecting component or an ion concentration
detecting component comprising the polymer particles as described
in (12) or (13).
(23) A chromic article comprising the polymer particles as
15 described in any one of (14) to (16).
(24) The chromic article as described in (19), which is a
photochromic optical article.
EFFECT OF THE INVENTION [0022]
20 According to the present invention, it is possible to provide a sensor that can detect a change in environment such as temperature with high accuracy, is excellent in repeated use, and can be used stably even in an aqueous environment; polymer particles to be used to obtain such a sensor; and polymer particles to be used to obtain
25 a chromic material that can respond to a change in environment such as light and heat with high accuracy and is excellent in repeated use.

12
BRIEF DESCRIPTION OF THE DRAWINGS [0023]
The subjects as described above and other subjects, 5 characteristics, and advantages will be more apparent with reference to preferred embodiments as described later with the accompanying figures. [0024]
FIG. 1 is a view illustrating a change in fluorescence intensity 10 observed at an excitation wavelength of 396 nm of an aqueous dispersion containing temperature-sensitive fluorescent dye-containing copolymer particles.
FIG. 2 is a view illustratJ.ng a percentage of change in the fluorescence intensity at a pealt wavelength of the fluorescence 15 observed at an excitation wavelength of 396 nm of an agueous dispersion containing temperature-sensitive fluorescent dye-containing copolymer particles.
FIG. 3 is a view illustrating a change in fluorescence intensity observed at an excitation wavelength of 495 nmof an aqueous dispersion 20 containing temperature-sensitive fluorescent
dye/non-temperature-sensitive fluorescent dye-containing copolymer particles.
FIG. 4 is a view j.llustrating the oxygen responsiveness of the fluorescence intensity observed at an excitation wave],ength of 376 25 nm of an aqueous dispersion containing oxygen-sensitive fluorescent dye-containing copolymer particles.
FIG. 5 is a view illustrating the fluorescence intensity

13
observed at an excitation wavelength of 37 6 nm of an aqueous dispersion containing oxygen-sensitive fluorescent dye-containing copolymer partj.cles, oxygen-sensitive fluorescent dye THF solution.
FIG, 6 is a view illustrating a change in fluorescence intensity 5 observed at a wavelength of 420 nm depending on a change in pH when excited at 365 nm of an aqueous dispersion containing pH-sensitive fluorescent dye-containing copolymer particles and an aqueous solut-i.on of a pH-sensitlve fluorescent dye.
FIG. 7 is a view illustrating the excitation spectrum at a 10 fluorescence wavelength of 510 nra of an aqueous dispersion containing pyranine-containing copolymer particles at a pH of 3.1 to 11.3. FIG. 8 is a view illustrating the change in the ratio of a fluorescence intensity at an excitation wavelength of 451 nm to a fluorescence intensity at an excitation waveJ.ength 415 nm (excitation 15 waveJ.ength 451 nm/excitation wavelength 415 nm) when measuring a change in the fluorescent spectrum at a light wavelength of 510"nm due to a change in the pH of an aqueous dispersion containing pH-sensitive fluorescent dye-containing copolymer particles and an aqueous solution of a pH~sensitive fluorescent dye by scanning with 20 excitation light in the range of 300 nm to 500 nm.
FIG. 9 is a photographic view illustrating the colored state (a) and the decolored state (b) of each of the film (i) and the film (ii) -
25 DESCRIPTION OF EMBODIMENTS [0025]
Hereinafter, the embodiments of the present invention will be

14
described In detail. [0026]

The polymer particles of the present inventi.on comprise the 5 following components (a) and (b), and have an average particle
diameter of 50% by volume of equal to or more than 1 nm and equal to or less than 1000 nm:
(a) an am.phiphilic polymer; and
(b) a compound exhibiting a change in fluorescence
10 characteristics in response to a change in a specific environment. [0027]
Hereinafter, the (a) amphiphilic polymer will be described. The amphiphilic polymer is a polymer having a hydrophobic group and a hydrophilic group. Examples of a method for obtaining the
15 amphiphilic polymer include a synthesis method of copolymerization of a hydrophilic polymer and a hydrophobic polymer, and a method" of grafting either one of a hydrophobic polymer or a hydrophilic polymer to the functional group of the other. Examples of the hydrophobic polymer include polyolefins, polyacrylates or polymethacrylates
20 having a mesogen side chain, a long alkyl side chain, or a hydrophobic side chain, polystyrenes, and vinyl polymers. Examples of the hydrophilic polymer include polyethylene oxide, polypropylene oxide, polyvinyl alcohols, polyacrylic acids, polymethacrylic acids, polyacrylamides, polyacrylates having a hydrophilic side chain,
25 polymethacrylates having a hydrophilic side chain, and polysaccharides.
When dispersed in a dispersion medium such as water, the

15
amphiphilic polymers of the present invention preferably have a constant particle diameter regardless of the dilution concentration. [0028]
[Terminally Branched Copolymer] 5 The (a) amphiphilic polymer of the present invention is preferably a terminally branched copolymer having a structure represented by the following general formula (1). [0029]
X^—C—CH—X^ A
10 [0030]
Wherein, in the formula (1), A represents a polyolefin chain; R^ and R'^ each represent a hydrogen atom or an allcyl group having 1 to 18 carbon atoms, and at least one of R"^ and R^ is a hydrogen atom; and X"'" and X^ are the same as or different from each other and each
15 represent a group containing a linear or branched polyalkylene glycol group. [0031]
The number average molecular weight of the terminally branched copolymer represented by the general formula (1) is equal to or less
20 than 2.5 x 10^, preferably equal to or less than 1.5 x 10^, and more preferably equal to or less than 4.0 x lO'^, and preferably equal to or more than 5.5 x 10^, and more preferably equal to or more than 8 X 10^. The number average molecular weight is represented by the sum of the number average molecular weight of the polyolefin chain

16
represented by A, the number average molecular weight of the polyalkylene glycol group represented by X^' and X^, and the molecular weight of the R^, R'', and C2H portions. [0032] 5 If the number average molecu.lar weJ.ght of the terminally
branched copolymer is in the above range, it is preferable since the stability of particles in the dispersion tends to be excellent when the terminally branched copolymer particles are used as a dispersoid, the dispersibility in water and/or a solvent which dissolves a part
10 of water or dissolves all of water in an arbitrary ratio tends to be excellent, and preparation of the dj.spersion becomes easy. [0033]
The polyolefin chain represented by A in the general formula {1} is formed by polymerizing an olefin having 2 to 20 carbon atoms.
15 Examples of the olefin having 2 to 20 carbon atoms include a-olefins such as ethylene, propylene, 1-butene, and 1-hexene. In the present invention, the polymer may be a homopolyraer or copolymer of these olefins, or even a product of copolymerization with other polymerizable unsaturated compounds in the range in which the
20 properties are not impaired. Among these olefins, particularly preferred are ethylene, propylene, and 1-butene. [0034]
The number average molecular weight measured by gel permeation chromatography (GPC) of the polyolefin chain represented by A in the
25 general formula {1} is from 400 to 8000, preferably from 500 to 4000, and more preferably from 500 to 2000. Here, the number average molecular weight is a value in terms of polystyrene standards.

17
[0035]
When the number average rnolecular weight of the polyolefin chain represented by A is in the above range, it is preferable since the crystallinity of the polyolefin portion tends to be high, the 5 stability of the dispersion tends to be better, and preparation of the dispersion tends■to be easy due to low melt viscosity. [0036]
The ratio of the weight average molecular weight (Mw> to the number average molecular weight (Mn), both measured by GPC, of.the
10 polyolefin chain represented by A in the general formula (1), that is, the molecular weight distribution (Mw/Mn), is not particularly limited and is usually from 1.0 to a few tens, more preferably equal to or less than 4.0, and still more preferably equal to or less than 3.0.
15 When the molecular weight distribution (Mw/Mn) of the polyolef j,n chain represented by A in the general formula (1} is in the above range, it is preferable in view of the shape of particles in the dispersion and the uniformity of the particle diameter. [0037]
20 According to GPC, the weight average molecular weight (Mw) , the number average molecular weight (Mn) and the molecular weight distribution (Mw/Mn) of the polyolefin chain represented by A may be measured using, for example, a GPC-150 manufactured by Millipore Corporation under the following conditions.
25 Separating column: TSK GNI! HT (column size: diameter of 7.5 mm, length: 300 mm)
Column temperature: 140"C

18
Mobile phase: ortho-dichlorobenzene (manufactured by Wako Pure Chemical Industries, Ltd.)
Anti-oxidant: 0.025% by mass of butylhydroxytoluene {manufactured by Takeda Pharmaceutical Co., Ltd.) 5 Flow rate: 1.0 ml/min
Sample concentration: 0.1% by mass Sample injection amount: 500 pi Detector: differential refractometer [0038] 10 Incidentally, the molecular weight of the polyolefin chain represented by A may be measured by measurj.ng the molecular weight of the polyolefin having an unsaturated group at one terminal as described later and subtracting the corresponding amount of the terminal molecular weight. 15 [0039]
R^ and R^ are each a hydrogen atom or a hydrocarbon group having I to 18 carbon atoms, which is a substituent bonded to a double bond of the olefin constituting A and preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Preferred examples of the 20 alkyl group include a methyl group, an ethyl group, and a propyl group. [0040]
In the general formula (1) , X^ and X^ are the same as or different from each other and each represent a linear or branched polyalkylene glycol group having a number average molecular weight of 50 to 10000, 25 A branched embodiment of the branched polyalkyleneglycol group is a branch linked through a polyvalent hydrocarbon group or a nitrogen atom, and the like. Examples thereof include a branch from a

19
hydrocarbon group bonded to two or more nitrogen atoms, oxygen atoms, or sulfur atoms in addition to the main skeleton, a branch from a nitrogen atom bonded to two alkylene groups in addition to the main skeleton, and the like, 5 [0041]
When the number.average molecular weight of the polyalkylene glycol group is in the above range, it is preferable since the dispersd.bility of the dispersion tends to be better and preparation of the dispersjon becomes easy due to the low melt vi.scosity. 10 [0042]
x' and X^ in the general formula (1) have the aforementioned structure, whereby polymer particles composed of a terminally branched copclymer having an average particle diameter of 50% by vo].ume of equal to or more than 1 nm and equal to or less than 1000 15 nm is obtained without using a surfactant. [0043]
In the general formula (1), preferred examples of X and X , which may be the same as or different from each other, include a group represented by the general formula (2) or (4)'. 20 [0044]
E—X^ (2)
[0045]
Wherein, in the formula (2), E represents an oxygen atom or a sulfur atom; and X'^ represents a polyalkylene glycol group or a group 25 represented by the general formula (3), [0046]

20
3
m (3)
[0047]
wherein, in the formula {3), R^ represents an (m+1)-valent hydrocarbon group; Gs are the same as or different from each other 5 and each represent a group represented by -OX^ or -NX^'X^ (X'^ to X^ each represent a polyalkylene glycol group); and m is the bonding number for R"^ to group G, and represents an integer of 1 to 10. [0048]
(4)
10 [0049]
Wherein, in the formula (4) , X^ and X^ are the same as or different
from each other and each represent a polyalkylene glycol group or
a group represented by the general formula (3).
[0050] 15 In the general formula (3), the group represented by R^ is an
(m+l)-valent hydrocarbon group havj.ng 1 to 20 carbon atoms, m is
1 to 10, preferably 1 to 6, and particularly preferably 1 to 2.
[0051]
Preferred examples of the general formula (1) include a 20 terminally branched copolymer in which, in the general formula (1),
one of x'" and X^ is a group represented by the general formula (4) .
More preferred examples include a terminally branched copolymer in
which one of X^ and X^ is a group represented by the general formula

21
(4) and the other is a group represented by the general formula (2) . [0052]
Other preferred examples of the general formuJ.a (1) include a terminally branched copolymer in which, in the general formula (1), 5 one of X"^ and X^ is a group represented by the general formula (2), and still more preferred examples include a terminally branched copolymer in which both X"'" and X^ are each a group represented by the general formula (2). [0053] 10 A more preferred structure of the general formula (4) is a group represented by the general formula (5}. [0054]

-N' ^O'

(5)

O
[0055]
15 Wherein, in l:he formula {5) , X^ and X^° are the same as or different from each other and each represent a polyalkylene glycol group; and Q'' and Q^ are the same as or different from each other and each represent a divalent hydrocarbon group. [0056]
20 The divalent hydrocarbon group represented by Q""" and Q^ in the general formula (5) is preferably a diva].ent alkylene group, and more preferably an alkylene group having 2 to 20 carbon atoms. The alkylene group having 2 to 20 carbon atoms may have or may not have substituont(s), and examples of the alkylene group include an

22
ethylene group, a methylethylene group, an ethylethylene group, a dimethylethylene group, a phenylethylene group, a chloromethylethylene group, a bromomethylethylene group, a methoxymethylethylene group, an aryloxymethylethylene group, a 5 propylene'group, a trimethylene group, a tetramethylene group, a hexamethylene group, and a cycJ.ohexylene group. The alkylene group is preferably a hydrocarbon based alkylene group, particularly preferably an ethylene group or a methylethylene group, and more preferably an ethylene group. Q'' and Q'^ may be one alkylene group, 10 or may be a mixture "of two or more kinds of alkylene groups. [0057]
A more preferred structure of X and X^ represented by the general formula (1} is a group represented by the general formula (6). [0058]
O—X^^ (e)
15
[0059]
Wherein, in the general formula (6), X-'--'- represents a polyalkylene glyool group. [0060]
20 The polyalkylene glycol group represented by X"^ to X^"'" is a group obtained by the addition polymerization of alkylene oxide, Examples of the alkylene oxide constituting the polyalkylene glycol group represented by X"^ to X"'"^ include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin,
25 epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. Among these, preferred are propylene oxide, ethylene oxide, butylene oxide, and styrene oxide, more preferred are propylene oxide and

23
ethylene oxide, and partJ.cuJ.arly preferred is ethylene oxide. The polyalkylene glycol group represented by X^ to X^"" may be a group obtained by homopolymerization of these alkylene oxides, or may be a group obtained by copolymerization of two or more kinds of alkylene 5 oxides. Preferred examples of the polyalkylene glycol group include a polyethylene glycol group, a polypropylene glycol group, and a group obtained by copolymerization of polyethylene oxide and polypropylene oxide, and particularly preferred examples of the group include a polyethylene glycol group.
10 [0061]
When X"* and X^ in the general formula (!) have the aforementioned structure, it is preferable since the dispersibility of water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio becomes better when the terminally branched
15 copolymer of the present invention is used as a dispersoid. [0062]
As the terminally branched copolymer which can be used in the present invention, it is preferable to use a polymer represented by the following general formula (la) or (lb) '.
20 [0063]


R9
Oi-H 7 R« m
Oj-H
R6 j
(1 a)

[0064]
Wherein, in the formula (la) , R'^ and R"' each represent a hydrogen

24

10
15

atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R'' and R^ is a hydrogen atom, and the alkyl group is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms;
R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R^ is a hydrogen atom;
1 + m represents an integer of equal to or more than 2 and equal to or less than 450, "and preferably equal to or more than 5 and equal to or less than 200; and
n represents an integer of equal to or more than 20 and equal to or ],ess than 300, and preferably an j.nteger of equal to or more than 25 and equal to or less than 200. [0065]


(1 h)

20

[0066]
Wherein, in the formula {lb} , R* and R^ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R^ and R^ is a hydrogen atom; and the al.kyl group is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1, to 3 carbon atoms;
R^ and R' each represent a hydrogen atom or a methyl group, and

25

10

at ].ea3t one of R'' and R' is a hydrogen atom; R^ and R^ each represent
P. 0
a hydrogen atom or a methyl group, and at least one of R and R is a hydrogen atom; R'"' and R"'"^ each represent a hydrogen atom or a methyl group, and at least one of R^*^ and R'^ is a hydrogen atom;
I + m + o represents an integer of equal to or more than 3 and equal to or less 450, and preferably equal to or more than 5 and equal to or less than 200; and
n represents an integer of equal to or more than 20 and equal to or less than 300, and preferably equal to or more than 25 and equal to or less than 200. [0067]
As the polymer represented by the general formula (lb) , a polymer represented by the following general formula (Ic) is more preferably used.

15 [0068]

(1 c)
[0069]
Wherein, in the formula (lc>, 1 + m + o and n are the same as those in the general formula (lb). 20 [0070]
The number (n) of ethylene units of the polyethylene chain is calculated by dividing the number average molecular weight (Mn) of the polyolefin chain represented by A j,n the general formula (1) by

26
the molecular weight of the ethylene unit. Further, the total number (1 + m or 1 + m + o) of ethylene glycol units of the polyethylene glycol chaj.n j.s calculated on the assumption that the weight ratio of the polymGr raw material to ethy.lene oxide in use during the 5 addition reaction to synthesize the polyethylene glycol group J.s the same as the ratio of the polymer raw material to the number average molecuJ.ar weight (Mn) of the polyethylene glycol group. [0071]
For example, i.n the terminally branched copolymer (T) obtained
10 in Synthesis Example 1 of this Example, since the weight ratio of the polymer raw material (I) to ethylene oxide in use is 1:1, Mn of the polymer raw material (I) is 1223 and Mn of an extended ethylene gj.ycoi unit also becomes 1223. The total number (l+m-i-o) of ethylene glycol units of the polyethylene glycol chain can be calculated by
15 dividing this value by the molecular weight of the ethylene glycol unit, [0072]
Furthermore, n, 1 + m, or 1 + m + o can also be measured by "^Pi-NMR. For example, in the terminally branched copolymer (T) obtained in
20 Synthesis Examp],e 1 and particles in the dispersion system containing the copolymer (T), it can be calculated from the integrated value for the methylene group of the polyolef in chain represented by A (shift value: 1. 06 ppm -1.50 ppm) and the integrated value for the al]<;ylene group of the polyethylene glycol chain (shift value: 3.33 ppm - 3.72
25 ppm) when the integrated value for the methyl group at the terminal of the polyolef in cha,in represented by A in the general formula (1) (shift value: 0.88 ppm) is taken as three-protons.

27
[0073]
Specifically, the number average molecular weight of the polyolefin chain represented by A and the alkyJ.ene group can be calculated from the respective integrated values from'the facts that 5 the molecular weight of the methyl group is 15, the molecular weight of the methylene group is 14, and the molecular weight of the alkylene group is 44. n can be calculated by dividing the number average molecular weight of the polyolefin chain represented by A obtained herein by the moJ.ecular weight of the ethylene unit, while the total
10 number (1 + ra or 1 + m + o) of the ethylene glycol units of the
polyethylene glycol chain can be calculated by dividing the number average molecular weight of the alkylene group by the molecular weight of the ethyJ.ene glycol unit. [0074]
15 In the case where the polyolefin chain represented by A is
composed of an ethylene-propylene copolymer, n and 1 + m or 1 + m + o can be calculated by using both the content of propylene which can be measured by IR, "'"'C-NMR, or the like, and the integrated value in """H-NMR. In ^H-NMR, a method of using an InLernal standard is also
20 effective. [0075]
[Method for Preparing Terminally Branched Copolymer] The terminally branched copolymer can be prepared by the following methods.
25 First, in the target terminally branched copolymer, a polyolefin represented by the general formula (7} and having a double bond at one terminal is prepared as the polymer corresponding to the structure

28
of A represented by the general formula (1). [0076]
A
[0077] 5 Wherein, in the formula (7), A represents a polyolefin chain, and preferably a group having a number average molecular weight of 400 to 8000, obtained by the polymerization of an olefin having 2 to 20 carbon atoms; and R-'- and R^ are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R"^ and R^
10 represents a hydrogen atom. [0078]
This polyolefin may be prepared according to the following methods:
(1.1) A polymerization method of using a transition metal
15 compound having a salicylaldimine ligand as described in Japanese Unexamined Patent Publication No. 2000-239312, Japanese Unexamined Patent Publication No. 2001-2731, Japanese Unexamined Patent Publication No. 2003-73412, and the like, as the polymerization catalyst;
20 (1. 2) A polymerization method of using a titanium-based cata].yst comprising a titanium compound and an organic aluminum compound;
(1.3) A polymerization method of using a vanadium-based catalyst
comprising a vanadium compound and an organic aluminum compound; and
(1.4) A polymerization method using a Ziegler type catalyst
25 comprising a metallocene compound such as zirconocene and an organic

29
aluminum oxy compound (aluminoxane). [0079]
Among the methods (l.l) to (1.4), in particular, according to the method (1.1), the polyolefin can be prepared in a good yie].d, 5 In the method (1.1), the polyolefin having a double bond at one terminal can be prepared by polymerizing or copolymerizing the above-mentioned olefin in the presence of the transition metal compound having a salicylaldimine ligand. [0080]
10 The polymerization of olefin according to method (1.1) can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization, or a gas phase polymerization method. Detai].ed conditions and the like are already known and the polyolefin can be prepared by referring to the Patent
15 Documents above. [0081]
The molecular weight of the polyolefin obtained according to method (1.1) can be adjusted by adding hydrogen to the polymerization system, by varying the polymerization temperature, or by changing
20 the kind of catalyst in use. [0082]
Subsequently, the polyolefin is epoxidized, that is, the double bonds at the terminals of the polyolefin are oxidized, to obtain a terminal epoxy group-containing polymer represented by the general
25 formula (8). [0083]

30
[^ Q R^

A
[0084]
Wherein, in the .formula (8), A represents a polyolefin chain, and preferably a group having a number average molecular weight of 5 400 to 8000, obtained by the polymerization of an olefin having 2 to 20 carbon atoms; and R"' and R^ are each a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at ].east one of P} and R^ represents a hydrogen atom. [0085] 10 Such an epoxidation method is not particularly limited, but can be exempli.fied by the foJJ.owi.ng methods;
(2.1) Oxidation by peracids such as performic acid, peracetic
acid, and perbenzoic acid
(2.2) Oxidation by titanosilicate and hydrogen peroxide;
15 (2.3) Oxidation by a rhenium oxide catalyst such as
methyltrioxorhenium, and hydrogen peroxide;
(2.4) Oxidation by a porphyrin complex catalyst such as
manganese porphyrin and iron porphyrin, and hydrogen peroxide or
hypochlorite;
20 (2.5) Oxidation by a salen complex such as manganese salen, and hydrogen peroxide or hypochlorite;
(2.5) Oxidation by a TACN complex such as a manganese
triazacyclononane (TACN) complex, and hydrogen peroxide; and
(2.7) Oxidation by hydrogen peroxide in the presence of a Group

31
VI transition metal catalyst such as a tungsten compound, and a phase
transfer catalyst.
[0086]
Among the methods (2.1) to {2.1), the methods (2.1) and (2.7) 5 are particularly preferred in view of activity.
Further, for example, a terminal epoxy group-containing polymer having a low molecular weight Mw of about 400 to 600 that can be used is VIKOLOX'" (registered trademark, manufactured by Arkema Inc.). [0087]
10 It is possible to obtain a polymer (polymer (I)) in which various substituents Y""" and Y^ are introduced into a- and p-positions at the terminals of the polymer as represented by the general formula (9) by reacting various reaction reagents with the terminal epoxy group-containing polymer represented by the general formula (8)
15 obtained according to the methods above. [0088]
o1
Y1—c—C Y2 <3>
[0089]
Wherein, in the formula (9), A represents a polyolefin chain,
20 and preferably a group having a number average molecular weight of
400 to 8000, obtained by the polymerization of an olefin having 2
to 20 carbon atoms; R^ and R^ are each a hydrogen atom or an alkyl
group having 1 to 18^ carbon atoms, and at least one of R"'" and R^
1 ^
represents a hydrogen atom; and Y and Y are the same as or different

32
from each other and each represent a hydroxyl group, an amino group,
or the following general formulae (lOa) to (10c).
[0090]
E—R3-(T)^ (10 a)
5 [0091]
-N^R3-(T) J2 (low
[0092]

m
(1 Oc)
N—R^—(T) H
[0093]
10 Wherein, in the general formulae (10a) to (10c), E represents an oxygen atom or a sulfur atom; R"^ represents an (m+l)-valent hydrocarbon group; Ts are the same as or different from each other and each represent a hydroxyl group or an amino group; and m represents an integer of 1 to 10.
15 [0094]
For example, a polymer in which, in the general formula (9), both Y"*" and Y^ are each a hydroxyl group is obtained by the hydrolysis of the terminal epoxy group-containing polymer represented by the general formula (8), while a polymer i.n which one of Y^ and Y^ is an
20 amino group and the other is a hydroxyl group J.s obtained by the reaction with ammonia. [0095]
Furthermore, a polymer in which, in the general formula (9),

33
one of Y"'" and Y^ is a group represented by the general formula (lOa) and the other is a hydroxyl group is obtained by reacting the terminal epoxy group-containing polymer represented by the general formula (8) with a reaction reagent A represented by tho general formula (11a), 5 [0096]
HE—R3—(T),,, (11 a)
[0097]
Wherein, in the formula (11a), E represents an oxygen atom or
a sulfur atom; R^ represents an (m+l)-valent hydrocarbon group; Ts 10 are the same as or different from each other and each represent a
hydroxyl group or an amino group; and m represents an integer of 1
to 10.
[0098]
Furthermore, a polymer in which, in the general formula (9), 15 one of Y^ and Y^ is a group represented by the general formula (10b)
or (10c) and the other is a hydroxyl group is obtained by reacting
the terminal epoxy group-containing polymer with a reaction reagent
B represented by the general formula (lib)'or (lie).
[0099]

20

HN'-|RMT)m)2 (lib)
[0100]
H2N—R3-(T)^ (11,)
[0101]
Wherein, in the formulae (lib) and (lie), R'^ represents an

34
(m+l)-valent hydrocarbon group; Ts are the same as or different from each other and each represent a hydroxyl group or an amino group; and m represents an integer of 1 to 10. [0102] 5 Examples of the reaction reagent A represented by the general formula (11a) include glycerin, pentaerythritol, butanetriol, dipentaerythritol, polypentaerythritol, dihydroxybenzene, and trihydroxybenzene. [0103]
10 Examples of the reaction reagent B represented by the general formula (lib) or (lie) include ethanoIamJ.ne, diethanolamine, aminophenol, hexamethylcneimine, ethylencdiamine, diaminopropane, diaminobutane, diethylenetriamine, N- (aminoethyl) propanediaioine, iminobispropylamine, spermidine, spermine, triethylenetetramine,
15 and polyethyleneimine.
The addition reaction of an'epoxy compound with alcohols, or amines is well-known, and the reacti.on can be easily carried out according to a uyual method, [0104]
20 The compound represented by the general formula (1) can be
prepared by carrying out an addition polymerization of the alkylene oxide using the polymer (I) represented by the general formula (9) as a raw material. Examples of the alkylene oxide include propylene oxide, ethylene oxide, butylene oxide, styrene oxide, cyclohexene
25 oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. These may be used in combination of two or more kinds. Among these, propylene oxide, ethylene oxide, butylene

35
oxide, and styrene oxide are preferably used, and propylene oxide
and ethylene oxide are more preferably used.
[0105]
For the catalyst, the polymerization conditions, and the like, 5 known ring-opening polymerization methods for alkylene oxide can be used, and examples of obtaining a polyol by polymerizing various monomers are disclosed in "Revised Polymer Synthesis Chemistry," authored by Otsu Takayuki, Kagaku-Dojin Publishing Company, Inc., January 1971, pp. 172 - 180. Examples of the catalysl: used in,the
10 ring-opening polymerization include, as described in the above literature, Lewis acids such as AICI3, SbCls, BF3, and FeCla for cationic polymerization; hydroxides or alkoxides of alkali metals, amines and phosphazene catalysts for anionic polymerization; and oxides, carbonates, and alkoxides of alkaline earth metals, or
15 alkoxides of Al, Zn, Fe, or the like for coordination anionic
polymerization. Here, the phosphazene catalysts may be exemplified by those compounds described in Japanese Unexamined Patent Publication No. 10-77289, specifically the products resulting from changing the anion of commercially available
20 tetrakis[tris (dimethylamino)phosphoranylidenamino]phosphonium
chloride into an alkoxy anion by using an alkoxide of an alkali metal. [0106]
In the case where a reaction solvent is used, those inert to the polymer (I) and the alkylene oxide can be used, and examples of
25 the solvent include n-hexane, allcyclic hydrocarbons such as
cyclohexane, aromatic hydrocarbons such as toluene and xylene, ethers such as dioxane, and halogenated hydrocarbons such as

36
dichlorobenzene. [0107]
The amount of the catalyst to be used for the catalysts other than phosphazene catalysts is preferably in the range of 0.05 moles 5 to 5 moles, and more preferably in the range of 0. 1 moles to 3 moles, based on 1 mole of the polymer (1) as a raw material. The amount of phosphazene catalyst to be used is preferably from 1 x 10"^ moles to 5 X 10""'" moles and more preferably from 5 x 10~^ moles to 1 x 10"'" moles, based on 1 mole of the polymer (I), from the viewpoints of
10 a polymerization rate, economic efficiency, and the like, [0108]
The reaction temperature is usually from 25''C to 180°C and preferably from SO^C to ISCc, and although the reaction time varies depending on the reaction conditJ.ons such as the amount of the catalyst
15 to be used, the reaction temperature, the reactivity of olefins, or the like, it is usually from a few minutes to 50 hours, [0109]
The number average molecular weight of the terminally branched copolymer represented by the general formula (1) can be calculated
20 by a method of calculating it from the number average molecular weight of the polymer (I) represented by the general formula (8) as described above and the weight of the alkylene oxide to be polymerized, or a method of using nuclear magnetic resonance (NMR). [0110]
25 The polymer particles of the present invention, comprising such a terminally branched copolymer, have a structure in which the polyolefin chain portion represented by A in the general formula (1)

37
is oriented in an internal direction, and are rigid particles in which
this polyolefin chain portion has crystallinity.
[0111]
The polymer particles of the present invention can be dispersed 5 again in a ],iquid such as a solvent even after particles are taken out of the dispersion by drying since the polyolefin chain portion thereof has crystallinity. The polymer particles of the present invention are rigid particles in which the melting point of the polyolefin chain portion contained in the particles is no!: lower than
10 SO^C and preferably not lower than 90°C. [0I].2]
Examples 52 and 53 of Patent Document (the pamphlet of International Publication No. 2005/073282) disclose a method of obtaining micelles having an average particle diameter of from 15
15 nm to 20 nm using this terminally branched copolymer. However, the method disclosed in the document'is a method of using the toluene soluble fractj.on in which the terminally branched copolymer is fractionated into a toluene soluble portion and a toluene insoluble portion, and the polyethylene chain portion of the terminally
20 branched copolymer has a low molecular weight. Specifically, the terminally branched copolymer is melted under heating in the presence of toluene, and then a slurry iiquJ.d after cooling is separated by filtration and toluene is distilled off from the toluene solution, followed by drying, to obtain a polymer. The resultant polymer is
25 mixed with water, stirred while boiling under normal pressure, further stirred using ultrasonic waves, and cooled to room temperature.

38
[0113]
In polyethylene, there is a correlation between the molecular weight and the melting point such that a lower molecular weight indicates a lower melting point. Also, Examples 52 and 53 of the 5 Patent Document (the pamphlet of International Publication No.
2005/073282) disclose that the melting point of the toluene insoluble portion is not lower than lOO^C, and the melting point of the toluene soluble portion is around VO^C. Even though micelles disclosed in the Patent Document are cooled, it is possible to obtain particles
10 obtained by crystallizing the polyethylene chain portion, whereas it is not possible to obtain rigid particles since the melting point is too low giving insufficient crystal],inity. Furthermore, there are some points to be improved, for example, micelles are easily obtained by heating, but particle properties are easily lost due to
15 disintegrating particles. [0114]
On the other hand, the polymer particles of the present invention are. rigid particles with excellent crystallinity since the melting point of the polyolefi.n chain portion is in the aforementioned range,
20 and disintegration of particles is suppressed even under heating at a higher temperature, [0115]
Accordingly, in the production process and use situations for various uses as described J.ater, disintegration of partd.cles is
25 suppressed so that the yield of the products and the quality of the products are more stabilized without losing characteristics of the polymer particles of the present invention.

39
[0116]
Even when the polymer particles of the present invention are dispersed in a solvent or the like, the particle diameter is constant regardless of the dilution concentration. Namely, the polymer 5 particles are different from micelle particles dispersed in a liquid because the polymer partj.cles have redispersibility and uniform dispersion particle diameter. Further, the amphiphilic polymer particles of the present invention can be applied in pH sensing since they may be dispersed in water at a high concentration without the
10 addition of a surfactant as well as the additi on of anionic/cationic components (neutral region), unlike styrene-based emulsion particles, aery1-based emulsion particles, or the like,
In addition, the amphiphilic polymer particles of the present invention can be used in a buffer solution, and therefore, can inhibit
15 damage to cells to a least extent and can be applied in bio-iraaging uses. [0117]
Incidentally, the average particle diameter of 50% by volume of the polymer particJ.es of the present invention is preferably equal
20 to or more than 1 nm. Thus, the dispersion characteristics of the fluorescent material become uniform, thereby obtaining dispersion stability of the polymer particles themselves in a solvent. Further, the average particle diameter of 50% by voJ.ume is preferably equal to or less than 1000 nm, which can makes it possible to perform
25 bio-imaging in a microscopic region. Further, from the viewpoint of sensing local information in cells or of transparency of a coating component, the average particle diameter of 50% by volume is

40
preferably equal to or less than 500 nm, more preferably equal to or less than 100 nm, and still more preferably equal to or less than 30 nm. In the case of a use in a photochromic optical component, the average particle diameter of 50% by volume is necessarily equal 5 to or less than 30 nm so as to avoid the effects of light scattering, Furthermore, since the polymer particles of the present invention are amphiphilic polymer particJ.es, it is difficult for the particles to aggregate even when they have particle diameters of equal to or less than 30 nm. 10 [0118]
The particle diameter of the polymer particles is measured using a dynamic light-scattering Nanotrac particle size analyzer "Microtrack UPA-EX150, manufactured by Nikkiso Co., Ltd.". Specifically, the prepared dispersion is added dropwise to the 15 analyzer so as to have an appropriate concentration and uniformly dispersed, and then average particle diameters of 10%, 50%, and 90% by volume can be measured.
The shape ol the particle can be observed, for example, using a transmission electron microscope (TEM) after carrying out negative 20 staind.ng with phosphotungstic acid, [0119]
Hereinafter, the (b) compound exhibiting a change in fluorescence characteristics in response to a change in a specific environmental factor (hereinafter also referred to as a sensor 25 compound) will be described.
The sensor compound refers to a compound exhibiting a change in fluorescent characteristics as shown below in response to a change

41
in an environmental factor as shown below, provided that the change in the environmental factor and the change in the fluorescent characteristics are correlated.
Examples of the environmental factor include temperature, 5 pressure, oxygen, metals, and pH. In order to make the compound function as a sensor, the compound preferably senses a change in only one environmental factor, but does not sense a change in other environmental factors. In addition, it is a.lso preferable that the compound sense only a change in the temperature and a change in,the 10 pressure, but does not sense a change in other environmental factors. Examples of the fluorescent characteristics include a fluorescence intensity, a quenching speed, a fluorescent lifetime, and a fluorescence wavelength shift.
Examples of the sensor compound include compounds that exhibit 15 a change in the fluorescent characteristics, such as a
temperature-sensitive fluorescent dye, a pressure-sensitive fluorescent dye, an oxygen-sensitive fluorescent dye, a metal {metal ion)-sensitive fJuorescent dye, and a pH (acid and base)-sensitive fluorescent dye. 20 [0120]
First, the (b) compound exhibiting a change in fluorescence characteristics in response to a change in a specific environmental factor will be described.
[Temperature-Sensitive Fluorescent Dye] 25 Examples of the temperature-sensitive fluorescent dye for use in the present invention include compounds having a linear change in fluorescence intensity in response to temperature. Desirably,

42
in a predetermined temperature range, the compound exhibits a change in fluorescence intensity of preferably equal to or more than 0 .1%/1°C, and more preferably equal to or more than 1.0%/1''C. Suitably, used is a complex compound of a rare earth element selected from europium 5 (Eu), lanthanum (La), samarium (Sm), gadolinium (Gd), terbium (Tb) , dysprosium (Dy> , thulium (Tm), ytterbium (Yb), and lutetium (Lu) with p-diketone chelating compounds, or a complex compound of iridium (Ir) with aromatic compounds. Among these, preferred are a complex compound of europium with p-diketone chelating compounds and a 10 complex compound of "iridium (Ir) with aromatic compounds.
Specifically, tris(thenoyltrifluoroacetonate)europium (III) (Eu (III)(TTA)^) or a derivative (a hydrate or the like) thereof, tris(benzoylacetonate)europium (III) (Eu (III) (bac)3) , tris(dibenzoylmethanate)europium (III) (Eu (III) (dbm)3) , 15 tris(hexafluoroacetylacetonate)europium (III) (Eu (III) (hfacac)3) , tris (acetylacetonate)europium (III) (Eu (III) (acacjg), (1, lO-phenanthroline) tris (thenoyltrif ],uoroacetate) europium (III) (Eu (III) (TTA)3PHEN), and tris(2-phenylpyridine)iridJum(III) (Ir(lII) (ppy)3) , and in particular, in view of a high yield of 20 fluorescence at around room temperature, or the like,
tris(thenoyltrifluoroacetonate)europium (III) (Eu (III)(TTA)3) or a derivative (a hydrate or the like) thereof is most preferably used, [0121]
In the case where the temperature-sensitive fluorescent 25 dye-containing copolymer particles are immobilized with a
concentration difference, it is possible that a variation in the fluorescence intensity occurs, resulting in an error in a temperature

43
detecting element. The variation can be corrected by further incorporating a non-temperature-sensitivc fluorescent dye as a reference. Preferably, the non-temperature-sensitive fluorescent dye does not have a wavelength distribution overlapping that of the 5 fluorescence of the temperature-sensitive fluorescent dye used. In the case where an Eu complex is excited with light in the vicinity of 300 nm, fluorescence can be found in the vicinity of 600 nm (red light) . As a reference, a fluorescent dye having a fluorescence found at equal to or less than 500 nm (blue to green light) is preferred, 10 and examples of the "fluorescent dye include fluorescein and a
derivative thereof, a rhodamine derivative, and a cyanine derivative, and specifically fluorescein isothiocyanate (FITC) and rhodamine B. [0122]
[Pressure-Sensitive Fluorescent Dye] 15 Examples of the pressure-sensitive fluorescent dye include a dye having a fluorescence exhibiting a quenching property when sensing a pressure. Specific examples of such a pressure-sensitive fluorescent dye include perylene; metal porphyrin compounds such as platinum porphyrin and zinc porphyrin; 20 tris(thenoyltrifiuoroacetonato)europium (III) (Eu (III)(TTA)3) or a hydrate thereof, tris(benzoylacetonate)europium (III) (Eu (III) (bac)3) , tris(dibenzoylmethanate)europium (III) (Eu (III) (dbm)3) , tris(hexafluoroacetylacetonate)europium (III) {Eu (III) (hfacac}3) , tris(acetylacetonate)europium (III) (Eu 25 (III) (acac)3) ,
(1,10-phenanthroline)tris(thenoyltrifluoroacetate)europium (III) (Eu (III) (TTA)3PHEN) ; ruthenium (Ru) complexes such as

tris(2,2'-bipyridine)ruthenium(II) (Ru(II) (bpy) 3)and tris(2,2'-bipyrazine)ruthenium(II) (Ru(II) (bpz)3) ; and iridium (Ir) such as tris(2-phenylpyridineiridium(III) (Ir(III) (ppy)^) . [0123] 5 [Oxygen-Sensitive Fluorescent Dye]
Examples of the oxygen-sensitive fluorescent dye include a dye having a fluorescence exhibiting a quenching property due to oxygon. Specific exarapJ.es of such an oxygen-sensitive fluorescent dye include metal porphyrin compounds such as platinum porphyrin and zinc 10 porphyrin; tris(thenoyltrifluoroacetonate)europium (III) (Eu
(III) (TTA)^) or a hydrate thereof, tris(benzoylacetonate)europium (III) (Eu (III) (bac) 3) , tris (dibenzoylmethanate) europium (III) (Eu (III) (dbm)3) , tris(hexafluoroacetylacetonate}europium (III) (Eu (III)(hfacac)3), tris(acetylacetonate)europium (III) (Eu 15 (III) (acac)3) ,
(1,10-phenanthroline)tris(thenoyltrifluoroacetate)europium (III) {Eu (III) (TTA)3PHEN) ; ruthenium (Ru) complexes such as tris(2,2'-bipyridine)ruthenium(II) (Ru(II) (bpy) 3) and tris(2,2'-bipyrazine)ruthenium(II) (Ru (II) (bpz)3) ; and iridium (Ir) 20 such as tris(2-phenylpyridine)iridium(III) (Ir(III) (ppy)3) . [0124]
[Metal (Metal Ion)-Sensitive Fluorescent Dye, Metal (Metal Ion)-Sensitive Fluorescent Protein]
The metal-sensitive fluorescent dye is a dye showing 25 fluorescence by binding to metal ions such as Ca , Ni , Cu , Zn , and Co^"^, and representative examples of the metal-sensitive fluorescent dye include a Ca'^"''-sensitive fluorescent dye. Examples

45
of the Ca^''"-sensitive fluorescent dye include
4- {6-acetomethoxy-2, 7-di,ch].oro-3-oxo-9-xanthyl) -4 '-methyl-2, 2 ' - { ethylenedj.oxy) dianiline-N,N,N' ,N' -tetracetj.c acid tetrakis(acetoxymethyl) ester (Fluo-3, AM), 5 N-[4-[6-[(acetoxy}methoxy]-2,7-difluoro-3-oxo-3H-xanthen-9-yl]-2 - [2-[2-[bis[(acetoxy}methoxy]-2-oxoethyl], (acetoxy}methyl ester (Fluo-4, AM), and fJ.uorescent protein exhibiting a change in fluorescence intensity in response to the amount of metal j.ons. Specific examples of the fluorescent protej.n for use in the present
10 invention include GFP, GFPuv, AcGFP, AcGFPl, HcRedl, DsRed-Monomer, DsRed2, ZsGreenl, ZsGreenl-DR, ZsYellowl, DsRed-!i;xpress2, DsRed-Monomer, mCherry, mOrange2, AmCyan, ZsProSesor, tdTomato, mPJ.um, pHcRedl-DR, DsRed-Express-DR, and pTimer Vectors. [0125]
15 [pH (Acid or Base)-Sensitive Fluorescent Dye]
Examples of the pH-sensitive fluorescent dye include those exhibiting a change in fluorescence intensity depending on a change in the pH. Specific examples of the pH-sensitive fluorescent dye include pyranine, fluorescein diacetate, 5(6)-carboxyfluorescein
20 diacetate, 5-carboxyfluorescein diacetate, 6-carboxyfluorescein diacetate, and 2',7'-bis(carboxyethyl)-5(6)-carboxyfluorescein tetracetoxymethyl ester. [0126]
The weight ratio of the (a) amphiphilic polymer to the (b) sensor
25 compound :,s not parti.cularJ.y limited, but preferably, the ratio of (b) is from 0.01 parts by weight to 100 parts by weight with respect to 100 parts by weight of (a), and more preferably the ratio of (b)

is from 1 part by weight to 10 parts by weight with respect to 100
parts by weight of (a).
In the case of using (c) a fluorescent material as a reference,
the amount of the fluorescent material used is not particularly 5 limited, but the ratio of (c) is from 0.001 parts by weight to 10
parts by weight with respect to lOO parts by weight of (b) , and more
preferably the ratio of (c) is from 0.01 parts by weight to 1 part
by weight with respect to 100 parts by weight of (b).
[0127] 10 Next, the (b) compound exhibiting a change in light absorption
characteristics in response to a change in a specific environmental
factor (hereinafter also referred to as a chromic material or a chromic
dye) will be described.
Examples of the light absorption characteristics include an 15 absorption spectrum, a percentage of change of intensity in ],ight
absorbance at a specific wavelength, and a change speed in intensity
of light absorbance at a specific wavelength.
[0128]
[Photochromic Dye] 20 The photochromic dye exhibits a reversible change in the
molecule structure due to irradiation with light at a specific
wavelength, and thus a change in light absorption characteristics (absorption spectrum) . Examples of the photochromic dye for use in
the present invention include compounds exhibiting a change in light 25 absorption characteristics (absorption spectrum) with respect to
light at a specific wavelength. As the photochromic dye, known ones
can bo used, and examples of such a photochromic dye include

47
naphthopyran, chromene, spiropyran, spirooxazine, and
thiospiropyran, benzopyran, stilbene, azobenzene, thioindigo,
bisimidazole, spirodihydroindolidine, quinine, perimidine
spirocyclohexadicnone, viologen, fuigide, fulgimide, diarylethene, 5 hydrazine, anil, aryl disulfide, arylthiosulfonate, spiroperimidine,
and triarylinethane.
[0129]
[Thermochromic Dye]
The thermochromic dye exhibits a change in light absorption 3,0 characteristics (absorption spectrum) depending on temperature,
Examples of the thermochromic dye include leuco dyes, and
specifically, phthalide, phthalane, an acylleucomethylene compound,
fluoran, spiropyran, and coumarin. Specific examples of the fluoran
inc],ude 3,3' -dimethoxyfluoran, 3, 6-dimethoxyf luoran, 15 3,6-dibutoxyfluoran, 3-chloro-5-phenylamino-fluoran,
3-diethylamino-6-dimethylfluoran,
3-diGthylamino-6-methyl-7-chlorofluoran,
3-diethyl-7,8-benzofluoran,
3,3'-bis-(p-dimethyl-aminophenyl)-7-phenylaminofluoran, 20 3-diethylamino-6-methyl-7-phenylamino-fluoran,
3-diethylamino-7-phenyl-aminofluoran, and
2-anilino-3-methyl-6-diethylamino-fluoran. Similarly, examples of
the phthalide include
3,3 ',3 ' '-tris(p-dimethylamino-phenyl)phthalide, 25 3,3-bis(p-dimethyl-aminophenyl)phthalide,
3,3-bis(p-diethylamino-phenyl)-6-dimethylaminophthalide, and
3-(4-diethylamino)phenyl.

48
[0130]
Since such a change in the absorption spectrum is caused by a change in the molecule structures due to an acid-base reaction (protonation-deprotonation) of a molecule, a proton donor (also 5 referred to as a "color developing agent") that generates an acid according to the temperature can also be used.
Examples of the proton donor include phenols, azoles, organic acids, and esters and salts of the organic acids.
Examples of phenols are phenylphenol, bisphenol A, cresol, 10 resorcinol, chlorolucinol, p-naphthol, 1,5-dihydroxynaphthalene, pyrocatechol, pyrogallol, and a trimer of a
p-chlorophenol-formaldehyde condensate. Examples of azoles are benzotriaoles (for example, 5-chlorobenzotriazole, 4-laurylaminosulfobenzotriazole, 5-butylbenzotriazole, 15 dibenzotriazole, 2-oxybenzotriazole, and
5-ethoxycarbonylbenzotriazole), imidazoles (for example, oxybenzimidazole), and tetrazoles.
Examples of cjrganic acids include aromatic carboxylic acids (for example, salicylic acid, resorcyJ.ic acid, and benzoic acid) , and 20 aliphatic carboxylic acids (for example, stearic acid,
1,2-hydroxystearic acid, tartaric acid, citric acid, oxalic acid, and lauric acid).
Further, in order to control the reaction by a thermochromic dye and a color developer, a proton receptor for receiving an acid 25 depending on a temperature (also referred to as a "desensitizer") may also be used. Examples of the proton acceptor include polyalcohoJ.s, fatty acid esters, glycol ethers, and polyethylene

49
glycol type nonionic surfactants. [0131]
[Other Chromic Dyes]
Other examples of the chromic dye include an electrochromic dye 5 exhibiting a change in light absorption characteristics due to electricity (application of voltages), and a solvatochromic dye exhibiting a change in light absorption characteristics due to the kind of a solvent in contact, [0132] 10 The weight ratio of the (a) amphiphilic polymer to the (b) chromic dye is not particularly limited, but the ratio of (b) is preferably from 0.01 parts by weight to 100 parts by weight with respect to 100 parts by weight of (a) , and the ratio of (b) is more preferably from 1 part by weight to 10 parts by weight with respect to 100 parts by 15 weight of (a). [0133]
[Dispersion]
The dispersion of the present invention has the polymer particles in a dispersoid, in which the dispersoid is dispersed in 20 the form of particles in water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio.
In the present invention, the dispersion is a dispersion formed by dispersing the polymer particles, and includes any one of:
(1) a dispersion having the polymer particles, obtained during
25 the preparatj.on of the polymer particles,
(2) a dispersj.on formed by further dispersing or dissolving
other dispersoids or additives in a dispersion having the polymer

50
particles, obtained during the preparation of the polymer particles,
and
(3) a dispersion formed by further dispersing or dissolving
other dispersoids or additives in a dispersion having the polymer 5 particles while dispersing the polymer particles in water or an
organic solvent having an affinity for water.
Further, in the present specification, the dispersion
encompasses an aqueous dispersion,
[0134] 10 The content of the polymer particles in the dispersion of the
present invention is preferably 0.1% by mass to 50% by mass, more
preferably 1% by mass to 40% by mass, and still more preferably from
1% by mass to 20% by mass, with respect to 100% by mass of the entire
dispersion. 15 When the content of the polymer particles is in the above range,
the practical usability of the dispersion is good, the viscosity can
be appropriately maintained, and handleability becomes easier, and
therefore, such a content is preferable.
[0135] 20 Furthermore/ the average particle diameter of 50% by volume of
the particles d.n the dispersion of the present invention is preferably
equal to or more than 1 nm and equal to or less than 1000 nm, more
preferably equal to or more than 1 nm and equal to or less than 500
nm, still more preferably equal to or more than 5 nm and equal to 25 or less than 50 nm, and even more preferably equal to or more than
10 nm and equal to or less than 30 nm,
The average parti.cle diameter of 50% by volume of the particles

51
can be adjusted by" changing the structure and/or moJ.ecular weight of hydrophobic groups constituting the amphiphilic polymer, the structure and/or molecular weight of hydrophilic groups, or the like. For example, in the case where the amphiphilic polymer is the 5 terminally branched copolymer, average particle diameter of 50% by volume of the particles can be adjusted by changing the structure of a polyolefin portion and the structure of a terminally branched portion in the terminally branched copolymer. [0136]
10 Incidentally, the average particle diameter of 50% by volume in the present invention refers to a diameter of the particles at 50% of the cumulative volume when the total volume is 100%, and can be measured by using a dynamic light-scattering particle diameter distribution measuring apparatus or a Microtrack particle size
15 distribution measuring apparatus.
In addition, the shape of the particle can be observed, for example, using a transmJ.ssion electron microscope (TEM) after carrying out negative staining with phosphotungstic acid, [0137]
20 The dispersion in the present invention is obtained by
dispersj.ng the polymer particles in water and/or a solvent, which dissolves a part of water or dissolves all of water in an arbitrary ratio.
The water is not particularly limited, and distilled water, ion
25 exchange water, city water, water for industrial use, or the like can be used. Distilled water and ion exchange water are preferabJ.y used.

52
[0138]
The solvent which dissolves a part of water or dissolves a]..l of water in an arbitrary ratio is an organic solvent having affinity for water and is not particularly limited as long as the polymer 5 particles can be dispersed therein, and examples thereof include ethylene glycol, tetraethylene glycol, isopropyl alcohol, acetone, acetonitrile, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, and dimethylimidazolidinone. [0139]
10 Preparation of dispersion in the present invention can be
carried out by a method of physically dispersing the polymer particles in water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio by a mechanical shearing force. [0140]
15 The dispersion method is not particularly limited, and various dispersion methods can be used. Specifically, there can be mentioned a method of dispersing the polymer particles with a high-pressure homogenizer, a high-pressure homomixer, an extrusion kneader, an autoclave, or the like in a mclten state after mixing the amphiphilic
20 polymer, water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio, and a sensor compound, a method of jet grinding at a high pressure, and a method of spraying from an aperture. Also, there can also be used a method of dispersing the terminally branched copolymer using a high-pressure homogenizer,
25 a high-pressure homomixer, or the like by mixJ.ng water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio after dissolving the amphiphilic polymer and the

53
sensor compound in a solvent other than water in advance. At this time, a solvent used for dissolution of the amphiphilic polymer and the sensor compound is not particularly limited as long as the amphiphilic polymer and the sensor compound are dissolved, but 5 examples of the solvent include toluene, cyclohexane, and the
aforementioned organic solvents having an affinity for water. In the case where it is not preferable that an organic solvent other than water be incorporated into the dispersion, the organic solvent can be removed by operations such as distillation or the like.
10 [0141]
Further, for example, the dispersion can also be obtained by mixing a dispersion obtained by dispersing the amphiphilic poJ.ymer in a dispersion medium such as water with a sensor compound, heating it with stirring whiJ.e applying a shearing force at a temperature
15 of not lower than lOO^C and preferably from 120"C to 200°C in an autoclave eguipped with a sti.rrer capable of applying a shearing force to make the amphiphilic polymer into a molten state initially, and mixing the sensor compound with the amphiphilic polymer to incorporate the sensor compound into the amphiphilic polymer
20 particles for redispersion. [0142]
When the temperature is in the above range, the amphj.philic polymer is easily dispersed because the amphiphilic polymer j,s in a molten state, and the amphiphilic polymer is hardly deteriorated
25 by heating, and therefore, such a temperature range is preferabJ.e, [0143]
The time required for melting, incorporation of the sensor

54
compound, and red!spersing varj.es depending on the dispersion temperature or other dispersion conditions, but it is about 1 minute to 300 minutes. [0144] 5 The dispersion can be sufliciently carried out during the
aforementioned stirring time, and the amphiphilic polymer is hardly deteriorated; therefore, such a time is preferable. After the reaction, it is preferable to maintain the state of the shearing force as applied until the temperature in the dispersion becomes not higher
10 than lOCc and preferably not higher than 60°C. [01^5]
In the case where a sensor compound having a low solubility in water is to be incorporated in the amphiphilic polymer particles, the amphiphilic polymer particles and the sensor compound extracted
15 once by drying can also be melt-mixed in a hydrophobic solvent such as toluene, fol].owed by removing the solvent, and then redispersing by the method described above, [0146]
In the preparation of the dispersion for use in the present
20 invention, it is not essential to add a surfactant as described above, but, for example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like may also be present. [0147]
25 Examples of the anionic surfactant include a carboxylate, a simple alkyl sulfonate, a modified alkyl sulfonate, an alkyl allyl sulfonate, an alkyl sulfate ester salt, a sulfonated oil, a suJ.furJ.c

55
acid ester, a sulfonated fatty acid monoglyceride, a sulfonated alkanolamide, a sulfonated ether, an alkyl phosphate ester salt, an alkylbenzene phosphoric acid salt, and a naphthalenesulfonic acid-formalin condensate. 5 [0148]
Examples of the cationic surfactant include a simple amine salt, a modified amine salt, a tetraalkyl quaternary ammonium salt, a modified trialkyl quaternary ammonJ.um salt, a trialkylbenzyl quaternary ammonium salt, a modified trialkylbenzyl quaternary
10 ammonium salt, an alkyl pyridinium salt, a modified alkyl pyridinium salt, an alkyl quinolinium salt, an alkyl phosphonium salt, and an alkyl sulfoni.um salt.
Examples of the amphoteric surfactant include betaine, sulfobetaine, and sulfate betaine,
15 [0149]
Examples of the nonionic surfactant include a monoglycerin fatty acidester, a polyglycol fatty acid ester, a sorbitan fatty acid ester, a sucrose fatty ai:id ester, a fatty acid alkanolamidc, a fatty acid polyethylene glycol condensate, a fatty acid amide polyethylene
20 glycol condensate, a fatty acid alcohol polyethylene glycol
condensate, a fatty acid amine polyethylene glycol condensate, a fatty acid mercaptan polyethylene glycol condensate, an alkylphenol polyethylene glycol condensate, and a polypropylene glycol polyethylene glycol condensate.
25 These surfactants may be used singly or in combination of two or more kinds. [0150]

56
In the preparation of the dispersion for use in the present invention, a filtration step during the process may be carried out for the purpose of removing foreign materials or the like. In such a case, for example, a stainless steel filter (wire diameter: 0.035 5 mm, plain weave) of about 300 mosh may be arranged and pressure filtration (air pressure: 0.2 MPa) may be carried out. [0151]
The dispersion obtained according to the aforementioned method does not cause aggregation and precipitation even though the pH varies 10 from 1 to 13 due to addition of various acids or bases, for example, acids such as hydrochloric acid, sulfuric acid, and phosphoric acJ.d, or bases such as potassium hydroxide, sodium hydroxide, and calcium hydroxide. Furthermore, this dispersion does not cause aggregation and precipitation even in a wide temperature range such that heating 15 and refluxing or freezing and thawing under normal pressure may be repeatedly carried out, [0152]
Meanwhile, the organic solvent having an affinity for water in the method is not particularly limited as long as the dispersoid is 20 soluble, and examples of the organic solvent include ethylene glycol, tetraethylene glycol, isopropyl alcohol, acetone, acetonitrile, methanol, ethanol, dimethyl sulfoxide, dimethyIformamide, and dimethylimidazolidinone. In the case where mixing of the organic solvent into the dispersion is not desired, the organic solvent can 25 be removed by distillation or the like after the preparation of the dispersion containing the dispersoid. [0153]

57
For the dispersion in the present invention, when the termj.nally branched copolymer is contained in an amount of 100 parts by mass, the surfactant can be contained in an amount of 0.001 parts by mass to 20 parts by mass, preferably in an amount of 0.01 parts by mass 5 to 10 parts by mass, and more preferably in an amount of 0.1 parts by mass to 5 parts by mass.
When the content of the surfactant is in the above range, it is preferable since physical properties of the dispersion are excellent from the practical point of view, and the dispersion hardly 10 causes aggregation and precipitation. [0154]
Examples of the immobilization method for the sensor compound-or chromic material-containing polymer particles of the present invention include a method for dispersing the particles in a binder 15 according to a sol-gel method (Preparation Example 1), and a method for dispersing the particles in a resin for a binder (Preparation Example 2). [0155]
20 Specifically, the following steps are included.
Step (a): In the presence of the sensor compound- or chromic material-containing polymer particles, a sol-gel reaction of a metal alkoxide and/or a partial hydrolysis condensate thereof is carried out, 25 Step (b): Preparation of a coating film. [0156]
Hereinafter, the respective stops will be described in order.

58
[Step (a)]
In the step (a), specifically, the sensor compound- or chromic material-containing polymer particles (A) (hereinafter referred to as a component (A)), a metal alkoxide and/or a partial hydrolysis 5 condensate thereof (B) (hereinafter referred to as a component (B) ) , and water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio (C) (hereinafter referred to as a solvent (C)) are mixed to prepare a mixed composition, while a sol-gel reaction of the component (B) is carried out. t'urther, in
10 the mixed composition, a catalyst for a so.l-gel reaction (D)
(hereinafter referred to as a catalyst (D) ) may be included for the purpose of promoting the hydrolysis/polycondensation reaction of metal alkoxides. [0157]
15 More specifically, the mixed composition is prepared by adding the catalyst (D) , and further, if necessary, water to the component
(B) or a solution obtained by dissolving the component (B) in the
solvent (C) for stirring and mixing, performing a sol-gel reaction
of the component (B) , and adding the component (A) while continuously
20 performing the sol-gel reaction. The component (A) can be added as
an aqueous dispersion.
[0158]
Incidentally, the mixed composition can also be prepared by
adding an aqueous dispersion of the component (A) to the component 25 (B) or a solution having the component (B) dissolved in the solvent
(C) , folJ.owed by stirring and mixing, and then adding the catalyst
(D), and if necessary, water, followed by stirring and mixing.

59
[0159]
Moreover, in order to enhance the mechanical strength, it is generally preferable to increase the proportion of the metal oxide, but when the thickness of the coating film is high, defects such as 5 generation of cracks may occur in the process of formation of the coating film.in some cases. For example, in order to form a coating film having a thickness of equal to or more than 1 ym, as the weight ratio of the component (A) to the component (B) , the content of the component (B) is preferably from 10 parts by weight to 2500 parts
10 by weight and more preferably from 10 parts by weight to 1800 parts by weight, based on 100 parts by weight of the component {A). [0160]
[Metal Alkoxide and/or Partial Hydrolysis Condensate of Metal Alkoxide (B) ]
15 The metal alkoxide in the present invention indicates those represented by the following formula (12).
(R^^)XiM(OR^^)yi (12)
[0161]
In the formula (12), R-'-^ represents a hydrogen atom, an alkyl
20 group (a methyl group, an ethyl group, a propy], group, and the like) , an aryl group (a phenyl group, a tolyl group, and the like), a carbon-carbon double bond-containing organic group (an acryloyl group, a methacryloyl group, a vinyl group, and the like), a halogen-containing group (a ha].ogenated alkyl group such as a
25 chloropropyl group and a fluoromethyl group), or the like; R represents a lower aj.kyl group having 1 to 6 carbon atoms and preferably having 1 to 4 carbon atoms; and in xi and yi, x; + yi = 4

60
and xi represents an Integer of equal to or less than 2. [0162]
Examples of M include Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb, Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, 5 Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi, and rare earth metals, and preferabJ.y used are metals (alkoxide) which become colorless metal oxides in the sol-gel reaction, such as Si, Al, Zn, Zr, In, Sn, Ti, Pb, and Hf from the viewpoint of use as a coating film. Among the metals, preferably used arc silicon (Si), aluminum (A].), zirconium
10 (Zr), titanium (Ti) and the like, or these metals may be used in combination. Among these, a silicon compound is relatively low-priced and easily obtainab],e, and has hJ,gh industrial usefulness since the reaction slowly proceeds. Also, the component (B) may be a compound which becomes a metal oxide as described later by addition
15 of water and a catalyst to perform the sol-gel reaction. [0163]
Specific examples include alkoxysilanes such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetrapropoxysilane, tetraisopropoxysiJ.ane, methyl trimethoxysilane,
20 methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysi],ane, ethyltriethoxysilane, n-propyltrimethoxysJ.lane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, dimethyldimethoxysilane,
25 dimethyIdiethoxysilane, diphenyldiraGthoxysilanc, diphenyldiethoxysilane, vinyltrimethoxysilanc, vinyltrj.ethoxysilane, phenyltrimethoxysiJ.ane,

61
phenyltriethoxysilane, p-styryltrimethoxysilane,
3-inethacryloxypropylmethyldimethoxysilane,
3-methacryloxypropylmethyldiethoxysilane,
S-methacryloxypropyltriinethoxysilane, 5 3-methacryloxypropyltriethoxysilane,
3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane,
3-chloropropyltriethoxysilane, Irifluoromethyltrimethoxysilane,
and trifluoromethy.ltr.iethoxys.i.-lane, and aJ.koxy aluminum, alkoxy
zirconium, and alkoxy titanium corresponding to the alkoxysilanes. 10 Furthermore, in addition to these metal alkoxides, metal
alkoxides having various functional groups for R^^ as shown in the
following 1} to 4) can also be used.
[0164]
1) Compounds having an amino group and an alkoxysilyl group, 15 such as 3-aminopropyltrimethoxysilane,
3-aminopropyltriethoxysilane, 3-aminopropylinethyldiinethoxysilane,
S-aminopropylmethyldiethoxysilane,
N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 20 2-aminoethylaminomethyltrimethoxysilane,
3-aminopropyldiniethylethoxysilane,
2-{2-aminoethylthioethyl}triethoxysilane,
p-aminophenyltrimethoxysilane,
N-phenyl-3-aminopropylmethyldimethoxysilane, 25 N-phenyl-3-aminopropylmethyldiethoKysilane,
N-phenyl-3-aminopropyltrimethoxysilane, and
N-phenyl-3-aminopropyltriethoxysilane.

62
[0165]
2) Compounds having a glycidyl group and an alkoxysilyl group,
such as 3-glycidoxypropylpropyltrlmethoxysilane,
3-glycidoxypropylpropyltriethoxysllane, and
5 3-glycidoxypropylmethyldiethoxys.ilane.
3) Compounds having a thiol group and an alkoxysilyl group such
as 3-mercaptopropylmethyldimethoxysilane and
3-mercaptopropyltrimethoxysilane.
4) Compounds having a ureide group and an alkoxysilyl group such
10 as 3-ureidepropyltrimethoxysilane.
[0166]
In the present invention, as the metal alkoxide, in the above formula (12), preferred are an alkoxysilane in which M is silicon (Si) , alkoxy zirconium in which M is zirconium (Zr), alkoxy aluminum 15 in which M is aluminum {Al} , and alkoxy titanium in which M is titanium (Ti). [0167]
The partial hydrolysis condensate of metal alkoxide is a compound obtained by partial hydrolysis of one or more of these metal 20 alkoxides using the catalyst (D), and then polycondensation of the resulting hydrolyzate. The partial hydrolysis condensate of metal alkoxide is for example, a partial hydrolysis polycondensation compound of metal alkoxide. [0168] 25 In the present invention, as the partial hydrolysis condensate of metal alkoxide, preferred are a condensate of alkoxysilane, a condensate of alkoxy zirconium, a condensate of alkoxy aluminum, and

63
a condensate of alkoxy titanium. [0169]
[Water and/or Solvent which dissolves a part of water or dissolves all of water in an arbitrary ratio (C)] 5 In the mixed composition of the present invention, the solvent (C) is added-for the purpose of further hydrolysis of the component (B). [0170]
Incidentally, the solvent (C) encompasses both a solvent to be
10 used to obtain an aqueous dispersion by using the terminally branched
copolymer, and a solvent to be used in the case of mixing the aqueous
dispersion, the component (B) , and a catalyst (D) as described later.
The water is not particularly limited, and distilled water, ion
exchange water, city water, water for industrial use, or the like
15 can be used, distilled water or ion exchange water is preferably used. [0171]
The solvent which dissolves a part of water or dissolves all of water in an arbJ Lrary ratio is an organic solvent having an affinity for water, and is not particularly limited as long as a terminalJ.y
20 branched copolymer can be dispersed in the solvent. Examples of the solvent include methanol, ethanol, propyl alcohol, isopropyl alcoho]., acetone, acetonitrile, dimethylsulfoxide, dimethylformamide, dimethylimidazolidinone, ethylene glycol, tetraethylene glycol, dimethylacetamide, N-methy].-2-pyrrolidone, tetrahydrofuran,
25 dioxane, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-methoxyethanol (methyl celj.osolve) , 2-ethoxyethanol (ethyl cellosolve) , and ethyl acetate. Among these, preferred are methanol,

64
ethanol, propyl alcohol", isopropyl alcohol, acetonitrile, dimethyl sulfoxide, dimethylformamide, acetone, tetrahydrofuran, and dioxane since these have a high affinity for water. [0172] 5 Further, at the time of hydrolysis polycondensation of metal alkoxides, the reaction temperature is preferably equal to or higher than 1°C and equal to or lower than 100°C, and more preferably equal to or higher than 20''C and equal to or lower than 60°C, while the reaction time is preferably equal to or more than 10 minutes and equal
10 to or less than 72 hours, and more preferably equal to or more than 1 hour and equal to or less than 24 hours. [0173]
[Catalyst for Sol-Gel Reaction (D)] The mixed composition for use in the present invention may
15 contain a material as shown beJ.ow, which can act as a catalyst for the hydrolysis polycondensation reaction, for the purpose of promoting the reaction in a hydrolysis polycondensation reaction of metal alkoxide. [0174]
20 Those used as the catalyst for the hydrolysis polycondensation reaction of metal alkoxide are the catalysts used in general sol-gel reactions, which are described in "Recent Technology for Functional Thin Film Production According to Sol-Gel Method" (Hirashima, Hiroshi, Comprehensive Technology Center Co., Ltd., p. 29), "Science of
25 Sol-Gel Method" (Sakka, Sumio, Agne Shofu, p. 154}, or the like. [0175]
Examples of the catalyst (D) include an acid catalyst, an alkali

65
catalyst, an organic tin compound, and metal alkoxides such as titanium tetraisopropoxide, diisopropoxytItanium bis (acetylacetonate), zirconium tetrabutoxide, zirconium tetrakis (acetylacetonate) , alximinum triisopropoxide, aluminum 5 trisethylacotonate, and trimethoxyborane. [0176]
Among these catalysts, an acid catalyst and an alkali catalyst are preferably used. Specific examples of the acid catalyst include inorganic and organic acids such as hydrochloric acid, nitric acid,
10 sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid. Examples of the alkali catalyst include ammonium hydroxide; alkali metal hydroxides such as potassj.um hydroxide and sodium hydroxide; quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and
15 tetrabutylammonium hydroxide; ammonia; amines such as triethylamine, tributylamine, morpholine, pyridine, piperidine, ethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, and triethanolamine; and aminosilanes such as 3-aminopropyltriethoxysilane, and
20 N(2-aminoethyl)-3-aminopropyltrimethoxysilane. [0177]
From the viewpoint of the reactivity, it is preferable to use acid catalysts such as hydrochloric acid and nitric acid, with which the reaction proceeds relatively mildly. The amount of the catalyst
25 to be used is preferably equal to or more than about 0.001 moles and equal to or less than, about 0.05 moles, more preferably equal to or more than about 0. 001 moles and equal to or less than about 0, 04 moles,

66
and still more preferably equal to or more than about 0.001 moJ.es and equal to or less than about 0,03 moles, with respect to 1 mole of the metal alkoxide of the component (B). [0178] 5 The mixed composition may be used, for example, in the form of a sol-gel product obtained by a sol-gel reaction without removing the solvent (C) in the presence of the catalyst (D). [0179]
[Step (b)] 10 In the step (b) , an organic/inorganic composite such as a coating film is obtained by coating and drying the reaction solution (mixed composj.tion) obtained in the step (a) .
The organic/inorganic composite containing polymer particles
and metal oxides can be obtained, for example, in the form of a sol-gel
15 product obtained by coating the reaction solution (mixed composition)
to a base material, then heating the resultant for a predetermined
time to remove the solvent (C) , and completing the sol-gel reaction.
Alternatively, il; can also be obtained in the form of a sol-gel product
obtained by coating a sol-gel intermadiate obtained by the sol-gel
20 reaction without removing the solvent (C) to a base material, then
heating the resultant for a predetermined time to remove the solvent
(C) , and completing the sol-gel reaction in the mixed composition.
Incidentally, the state of the completion of the sol-gel reaction means ideally the state of all components forming an M-O-M 25 bond, but includes the state shifted to a solid (gel) state even though some alkoxyl groups ,(M-OR^) or M-OH groups remain, [0180]

67
That is, the metal oxide can be obtained from the component {B} by completion of the sol-gel reaction by heat-drying the mixed composition (reaction solution) to form a matrix mainly composed of this metal oxide. The coating film has a structure in which sensor 5 compound- or chromic material-containing polymer particles (A) are dj.spersed j.n. the matrix. [018].]
The metal oxide in the sol-gel product is a continuous matrix structure in the organic/inorganic composite. The metal oxj.de is
10 not particularly limited as described above, but the metal oxide as a coating iilra is preferably a continuous matrix structure in view of j.mprovement of mechanical properties and the like. Such a structure of the metal oxide is obtained by subj ecting a metal, aJ.koxide to hydrolysis and polycondensation, that is, a sol-gel reaction,
15 [0182]
As a method for preparing a composite of porous support and a film, a method of dipping the porous support in the mixed composition of the present Invention and drying the porous support while maintaining it at a predete.rmi.ned temperature can be exemplified.
20 [0183]
Examples of the porous support for use in the present invention include porous materials of ceramics such as silica, alumina, zirconia, and titania; metals such as stainless steel and alviminum; and paper and resin,
25 The heating temperature for completing the sol-gel reaction is equal to or higher th.an room temperature and equal to or lower than SOO^C, and more preferably equal to or higher than SCC and equal

68
to or lower than 200''C. ' The reaction time is equal to or more than 10 minutes and equal to or less than 72 hours, and more preferably equal to or more than 1 hour and equal to or less than 24 hours. [0184] 5
Preparation Example 2 is an example in which the sensor compound-or chromic material-containj.ng polymer particles (A) are dispersed in a resin for a binder. The dispersing method is not particularly limited, but examples of the method include a method in which an
10 aqueous dispersion of the sensor compound- or chromic
material-containing polymer particles (A) is mixed with an aqueous solution of a water-soluble binder resin or an aqueous dispersion (emulsion) of film-forming binder resin particles, followed by heating and drying; and a method in which an aqueous dispersion of
15 the sensor compound- or chromic material-containing polymer
particles (A) is recovered as powder by volatizing moisture from the particles using a method of freeze-drying, spray-drying, or the like, then redispersed in a binder resin (varnish) dissolved in an organi.c solvent or a binder resin precursor monomer, followed by heating and
20 drying, and if necessary, subjected to a curing treatment. Hereinafter, the resin for a binder will be described. [0185]
The resin for a binder for use in the present embodiment is not particularJ.y limited. For example, examples of the resin include
25 a thermosettj,ng resin that cures by heating, a photocurable resin that cures by irradiation with .IJ.ght such as ultraviolet rays, a thermoplastic resin, and a water-soluble resin. Among these,

69
preferred are film-forming polyolef in-based, poly (meth) acrylic acd.d ester-based, polystyrene-based, polyurethane-based, polyvinyl alcohol-based, and polyvinylacetal-based polymers. [0186] 5 Examples of the thermosetting resin and the photocurable resin incJ.ude an epoxy resin, an unsaturated polyester resin, a phenol resin, a urea-melamine resin, a polyurethane resin, a polythiourethane resin, a silicone resin, a diallyl phthalate resin, an allyl diglycol carbonate resin, and a thermosetting polyimide resin,
10 [0187]
Examples of the epoxy resin include various types of epoxy resins, for example, glycidyl ether type epoxy resins such as a bisphenol A type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a cyclic aliphatic type epoxy resin, a novolac
15 type epoxy resin, a naphthalene type epoxy resin, and a
dicyclopentadiene type epoxy resin. Examples of the unsaturated polyester resin include an orthophthalic acid-based polyester resin, an isophthalic acid-based polyester resin, a terephthalic acid-based polyester resin, an alicyclic unsaturated acid-based polyester resin,
20 a fatty saturated polyester resin, a bisphenol-based polyester resin, a halogen-containing acid-based polyester resin, and a halogen-containing bisphenol-based polyester resins. Examples of the phenol resin include phenol resins such as resol type resin and a novolac type resin.
25 [0188]
Examples of the thermoplastic resin include a polyo].efin resin, a polyvinyl chloride resin, a vinylidene chloride-based resin, a

70
polystyrene resin, an acrylonitrlle/butadiene/styrene copolymer resin, an acrylonitrile/styrene copolymer resin, a styrene-based block copolymer resin, a methacryllc resin, a polyvinyl alcohol resin (PVA) , a polyv.lnyl acetal resin (PVB) , a polyacetal resin, a polyamlde 5 rosin, a polycarbonate resin, a modified polyphenyleneether resin, a thermoplastic polyester resin, a fluorine resin, a polyphenylenesulfide resin, a polysulfone resin, an amorphous arylate resin, a polyetherimide resin, a polyethersulfone resin, a polyetherketone resin, a liquid crystal polymer resin, a
10 po],yamidimide resin, a thermoplastic polyimide resin, and a syndiotactic polystyrene resin. [0189]
Examples of the polyolefin resin include a polyethylene resin, a polypropylene resin, an a-olefin copolymer resin, a polybutene-1
15 resin, a polymethylpentene resin, a cyclic olef in-based polymer resin, an ethylene/vinyl acetate copo.lymer resin, an ethylene/methacrylic acid copolymer resin, and an ionomer. [0190]
Examples of the polyamlde resin include Nylon 6, Nylon 66, Nylon
20 11, and Nylon 12. [0191]
Examples of the thermoplastic polyester resin include a polyethylene terephthalate resin, a polybutylene terephthalate resin, a polybutylenesuccinate resin, and a polylactic acid resin.
25 [0192]
Examples of the. fluorine resin include a polytetrafluoroethylene resin, a pertluoroalkoxyalkane resin, a

71
perfluoroethylenepropehe copolymer resin, an
ethylene/tetrafluoroethylene copolymer resin, a polyvinylidene
fluoride resin, a polychlorotrlfluoroethylene resin, an
ethylene/chlorotrifluoroethylene copolymer resin, a 5 tetrafluoroethylene/perfluorodioxole copolymer resin, and a
polyvinyl fluoride resin.
[0193]
Examples of the water-soluble resin include polyvinyl alcohol
(PVA), polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), ,and 10 derivatives thereof.
[0194]
As the film-forming polyolef in-based, po.ly(meth) acrylic acid
ester-based, polystyrene-based, or polyurethane-based resin
(aqueous emulsion), preferred are polymer particles having particle 15 diameters of 10 pm to 300 pm, which form a transparent coating fiJ.m
by drying and then heating at room temperature to equal to or lower
than lOO^C.
[0195]
The weight ratio of the sensor compound- or chromic 20 material-containing polymer particles (A) to the resin for a binder
is not particularly limited, but the ratio of the resin for a binder
is preferably from 10 parts by weight to 2500 parts by weight, and
more preferably from 10 parts by weight to 1800 parts by weight, with
respect to 100 parts by weight of (A). 25 [0196]
As a method for ^preparing a resin plate, a film, or a coating
film, dip coating, spin coating, spray coating, flow-down type

72
coating, blade coating, bar coating, die coating, or other appropriate methods may be used depending on an intended use, and the kind, shape, or the like of a substrate. As the substrate, porous supports can be used, in addition to molded products such as metals, 5 glass, ceramics, and polymers, sheets, films, or the like. [0197]

The polymer particles, the aqueous dispersion thereof, the mixed composition thereof or the organic/inorganic composite thereof in
10 the present invention can be used as sensors such as a temperature sensor, a pressure sensor, an oxygen sensor, a metal sensor, a pH sensor, or the like, an optical fiber type temperature detecting element, a temperature-sensitive paint, a temperature-sensitive film, an intrace]J.ular temperature measuring probe, or a bio-imaging
15 fluorescent probe. Further, the polymer particles can be suitably used as a temperature detecting component, oxygen detecting component or an ion concentration detecting component in a wide range of the medical, semiconductors, food, aviation, marine, and automotives field. Further, the polymer particles can be suitably used for
20 chromic articles such as photochromic spectacle lenses, light
modulating materials, display materials, ink materials, optical recording materials, and optical switches, in particular, photochromic optical articles. [0198]
25 It is believed that in the present invention, by incorporating a fluorescent material as a sensor compound into the above-described amphiphilic polymer particles having a small average particle

CLAIMS
1. Polymer particles comprising the following components (a) and
(b) and having an average particle diameter of 50% by volume of equal
5 to or more than 1 nm and equal to or less than 1000 nm:
(a) an amphiphilic polymer; and
(b) a compound exhibiting a change in fluorescence characteristics or light absorption characteristics in response to a change in a specific environmental factor.
10
2. Polymer particles comprising the following components (a) and
(b) and having an average particle diameter of 50% by volume of equal
to or more than 1 nm and equal to or less than 1000 nm: (a) an amphiphilic polymer; and 15 (b) a compound exhibiti.ng a change in fluorescence
characteristics in response to a change in a specific environmental factor.
3. The polymer particles according to claim 1 or 2, wherein
20 the (a) is a polymer particle represented by the following
general formula (1) and is a terminally branched copolymer havj.ng a number average molecular weight of equal to or less than 2.5 ;< lO'^,
X'—^C—CH—:
wherein, in the formula (1), A represents a polyolefin chain;

100
R"'" and R*^ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R^ and R^ is a hydrogen atom; and x'' and X^ are the same as or different from each other and each represent a group containing a linear or branched polyalkylene glycol 5 group.
4. The polymer particles according to claim 3, wherein
in the terminally branched copolymer represented by the general formula (1), X"^ and X^ are the same as or different from each other, 10 and are each a group' represented by either of the general formulae (2) and (4),
E—X3 (2)
wherein, in the formula (2), E represents an oxygen atom or a sulfur atom; and X^ represents a polyalkylene glycol group or a group 15 represented by the general formula (3),
.3_
^ (3)
wherein, in the formula (3} , R"' represents an (m+l> -valent hydrocarbon group; Gs are the same as or different from each other and each represent a group represented by -OX'' or -NX^X^ (X^ to X^ each 20 represent a polyalkylene glycol group); and m is the bonding number for R"^ to group G, and represents an integer of 1 to 10,
—N-X^ (4)
wherein, in the formula (4), X^ and X^ are the same as or different

101
from each other and each represent a polyalkylene glycol group or a group represontod by the general formula (3).
5. The polymer particles according to claim 4, wherein 5 the terminally branched copolymer is represented by the following general formula (la) or (lb),

R6 /I

(1


10
15

wherein, in the formula (la) , R and R"' each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one of R'' and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R'' is a hydrogen atom; 1 -i- m represents an integer of equal to or more than 2 and equal to or less than 450; and n represents an integer of equal to or more than 20 and equal to or less than 300,
R11

' m
(lb)
wherein, in the formula (lb) , R" and R'' each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and at least one

102
of R^ and R^ is a hydrogen atom; R^ and R^ each represent a hydrogen atom or a methyl group, and at least one of R^ and R' is a hydrogen atom; R" and R^ each represent a hydrogen atom or a methyl group, arid at least one of R" and R^ is a hydrogen atom; R"'"'' and R^^ each represent 5 a hydrogen atom or a methyl group, and at least one of R^° and R is hydrogen atom; 1 + m + o represents an integer of equal to or more than 3 and equal to or less than 450; and n represents an integer of equal to or more than 20 and equal to or less than 300.
10 6. The polymer particles according to any one of claims 1 to 5, wherein the average particle diameter of 50% by volume is equal to or more than 1 nm and equal to or less than 30 nm.
7 . The polymer particles according to any one of claims 1 to 6, wherein 15 the (b) is a temperature-sens J. tive fluorescent dye.
8. The polymer particles according to claim 7, further comprising
a non-tempej'ature-sensitive fluorescent dye as a reference for the temperature-sensitive fluorescent dye.' 20
9. The polymer particles according to claim 7 or 8, wherein
the temperature-sensitive fluorescent dye is selected from a complex compound of a rare earth element selected from europium (Eu) , j.anthanum (La), samarium (Sm) , gadolinium (Gd) , terbium (Tb) , 25 dysprosium (Dy), thulium (Tm), ytterbium (Yb), and lutetium (Lu) with j3-diketone chelating compounds, or a complex compound of iridium (Ir) with aromatic compounds.

103
10. The polymer particles according to claim 9, wherein
the temperature-sensitive fluorescent dye is
tris(thenoyltrifluoroacetonate)europium (III) (Eu (III)(TTA)3) or 5 a derivative thereof.
11. The polymer particles according to any one of c].aims 1 to 8,
wherein
the (b) is fluorescent protein. 10
12. The polymer particles according to any one of claims 1 to 6,
wherein the (b) is an oxygen-sensitive fluorescent dye or a
pH-sensitive fluorescent dye.
15 13. The polymer particles according to claim 12, wherein the oxygen-sensitive fluorescent dye is
tris(2-phenylpyridine)iridium(lll) (Ir(IlI)(ppy)3} or a derivative thereof, and the pH-sensitive fluorescent dye is pyranine.
20 14. The polymer particles according to any one of claims 1 to 6, wherein the (b) is a chromic material.
15. The polymer particles according to cJ.aim lA, wherein the chromic
material is a photochromic dye.
25
16. The polymer particles according to claim 15, wherein the
photochromic dye is a naphthopyran derivative.

104
17. An aqueous dispersion having the polymer particles according
to any one of claims 1 to 16 dispersed in water and/or a solvent which
dissolves a part of water or dissolves alJ. of water in an arbitrary
5 ratio.
18. A mixed composition comprising the following (A) , (B) , and (C) ,
and if necessary, (D):
(A) the polymer particles according to any one of: claims 1 to
10 16;
(B) a metal alkoxide and/or a partial hydrolysis condensate thereof;
(C) water and/or a solvent which dissolves a part of water or dissolves all of water in an arbitrary ratJ.o; and
15 (D) a catalyst for a sol-gel reaction,
19. An organic/inorganic composite comprising the polymer particles
according to any one of claims 1 to 16 and a metal oxide,
20 20. A sensor comprising any of the polymer particles according to any one of claims 1 to 16, the aqueous dispersion according to cj.aim 17, the mixed composition according to claim 18, and the organic/inorganic composite according to claim 19.
25 21, A temperature detectj.ng component comprising the polymer particles according to any one of claims 7 to 10.

1 05
22. An oxygcii detecting component or d.on concentration detecting component comprising the polymer particlea according to claim 12 or 13.
5 23, A chromic article comprising the polymer particles according to any one of claims 14 to 16.
24. The chromic article according, to claim 19, which j.s a photochromic optical article. ].0
Dated this 19.12.2014
[RANJNA MEHTA-DUTT]
OF REMFRY & SAGAR
ATTORNEY FOR TtlE APPLTCANT[S],

Documents

Application Documents

# Name Date
1 10911-delnp-2014-Correspondence Others-(21-04-2015).pdf 2015-04-21
1 POWER OF AUTHORITY.pdf 2014-12-23
2 10911-delnp-2014-Form-3-(21-04-2015).pdf 2015-04-21
2 PCT-IB-304.pdf 2014-12-23
3 FORM 5.pdf 2014-12-23
3 10911-delnp-2014-Correspondance Others-(10-02-2015).pdf 2015-02-10
4 FORM 3.pdf 2014-12-23
4 10911-delnp-2014-Form-1-(10-02-2015).pdf 2015-02-10
5 10911-DELNP-2014.pdf 2015-01-16
5 FORM 2 + SPECIFICATION.pdf 2014-12-23
6 DRAWING.pdf 2014-12-23
7 10911-DELNP-2014.pdf 2015-01-16
7 FORM 2 + SPECIFICATION.pdf 2014-12-23
8 10911-delnp-2014-Form-1-(10-02-2015).pdf 2015-02-10
8 FORM 3.pdf 2014-12-23
9 10911-delnp-2014-Correspondance Others-(10-02-2015).pdf 2015-02-10
9 FORM 5.pdf 2014-12-23
10 PCT-IB-304.pdf 2014-12-23
10 10911-delnp-2014-Form-3-(21-04-2015).pdf 2015-04-21
11 POWER OF AUTHORITY.pdf 2014-12-23
11 10911-delnp-2014-Correspondence Others-(21-04-2015).pdf 2015-04-21