JP2003253261A - Fluorescent substance, composite material, coating material, paint, ink, artificial skin, method for processing of information on contact with artificial skin, artificial luminescent skin, artificial luminescent hair, luminescent element, electronic device, luminescent system, display system, flexible luminescent material, ultrasonic luminescent substance, traffic label, luminescent method, method for producing composite material and method for producing luminescent element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material capable of emitting light with soft and light touch of human hand or finger. <P>SOLUTION: A first composite material is formed of a fluorescent substance such as SrAl<SB>2</SB>O<SB>4</SB>:Eu and an elastic material such as a polyester resin, wherein the content of the fluorescent substance is ≥30 wt.%. The composite material formed into a sheet having a thickness of ≤1 mm to provide a stress luminescent material. The stress luminescent material is used as an artificial skin, a luminescent system, a display system, etc. A second composite material is formed of a fluorescent substance such as SrAl<SB>2</SB>O<SB>4</SB>:Eu and a piezoelectric material. A luminescent element which can be controlled through an electric signal from the outside is realized by using the second composite material. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fluorescent substance, a composite material, a coating material, a paint, an ink, an artificial skin, an artificial skin contact information processing method, an artificial luminescent skin, an artificial luminescent hair,
The present invention relates to a light emitting device, an electronic device, a light emitting system, a display system, a flexible light emitting material, an ultrasonic light emitting substance, a traffic sign, a light emitting method, a composite material manufacturing method, and a light emitting device manufacturing method, for example, applied to the entertainment field and the optical field. And is suitable.

[0002]

2. Description of the Related Art In recent years, an aluminate-based material doped with a rare earth element has attracted attention as a fluorescent material, and active research has been conducted. As such an aluminate-based material, Eu-doped SrAl ₂ O ₄ (hereinafter referred to as “SrAl
₂ O ₄ : Eu ”) has received the most attention due to the report of the stress emission phenomenon as described later. Therefore, first, the history of research and development of SrAl ₂ O ₄ : Eu will be described with reference to prior art documents.

[0003] SrAl ₂ O _4: historical background of Eu SrAl ₂ O _4: Eu, there is a history that has been studied as a phosphor for a long time, has already been registered in the following patents 1960s, now known material It can be called a system. -Belgian Patent No. 1347459 (registered November 18, 1963) -US Patent No. 3294699 (December 27, 1966)
Day registration)

On the other hand, regarding academic papers, SrAl ₂ O
₄ : Papers reporting the basic crystal structure of Eu ・ FPGlasser and LSDGlasser, J.Am.Ceram.Soc., 46
(1963) 377-380 was published in 1963, and its fluorescent properties were investigated by several research institutes, and several papers have been published since 1968 as shown below.・ FCPallila, AKLevine and MR Tomkus, J. Electroc
hem.Soc., 115 (1968) 642-644 ・ G.Blasse and A.Bril, Philips Res.Repts., 23 (1968) 2
01-206 ・ G.Blasse, WLWanmaker and JWter Vrugt, J.Electr
ochem.Soc., 115 (1968) 673 ・ V.Abbruscato, J.Electrochem.Soc., 118 (1971) 930-933

After that, a crystallographic study of SrAl ₂ O ₄ crystal proceeded, and at a temperature higher than 650 ° C., un-distorted BaAl ₂ O ₄ type (a = 5.14Å, c = 8.47Å (700 ℃) is stable, and at lower temperatures, stuffed scale silica (stuffed)
tridymite) type monoclinic phase (a = 10.2)
0Å, b = 20.26Å, c = 8.42Å and γ = 6
0.53 °) is stable. ・ S.Ito, S.Banno, K.Suzuki and M.Inagaki, Z.Phyzik.Ch
em.Neue Folge, 105 (1977) 173-178, and the crystal system is a monoclinic crystal, a = 0.51947n.
The following papers have been published reporting m, b = 0.8836 nm, c = 0.8442 nm and β = 93.43 °.・ F.Hanic, TY Chemekova and J.Majling, J.Appl.Phy
s., 12 (1979) 243 ・ Von ARShulze and Hk.Muller-Buschbaum, Z.anorg.a
llg. Chem., 475 (1981) 205-210

Today, the crystal structures of the above two papers are basically considered, and JCPDS card No. 34-0379, a = 0.84424 nm and b = 0.8822n in the monoclinic system.
m, c = 0.51607 m and β = 93.415 °.

Long afterglow phosphor SrAl ₂ O ₄ : Eu + Dy
After that, although the development of the SrAl ₂ O ₄ : Eu phosphor can be subdued, the sensational development, which is definitely in the limelight, was carried out by Nemoto Special Chemical Co., Ltd.・ Http://www.nemoto.co.jp/inde x j.html They doped Dy as a co-activator to make them an amazing long-afterglow phosphor SrAl ₂ O ₄ : Eu + which is bright all night long.
Dy (N night light: product name "Luminova") was developed.・ Http://www.nemoto.co.jp/products/luminova/index.
html

Regarding this material and technology, patents have already been registered in Japan / US etc. as follows. S
The main difference from rAl ₂ O ₄ : Eu is that, in addition to Eu, another rare earth element, ie, Dy, which is another co-activator, is doped. -Patent No. 2543825 (Japanese Patent Laid-Open No. 7-11250) (registered July 25, 1996) -US Patent No. 5424006 (registered June 13, 1995) -European Patent No. 622440

Nemoto Special Chemical Co., Ltd. has been making various research reports on this material since its presentation at the Society of Phosphors in 1993 until today, and the following papers and explanations have been published. Are known.・ Tatsutsugu Matsuzawa, Nobuyoshi Takeuchi, Yasumitsu Aoki, Yoshihiko Murayama, 248th
Proc. Phosphor Res. Soc.
(1993.11.26) 7-13 ・ Yoshihiko Murayama, Nikkei Science (Scientific American Japanese version), 5 (1996) 20-29 ・ T.Matsuzawa, Y.Aoki, M.Takeuchi and Y.Murayama, JE
lectrochem.Soc., 143 (1996) 2670-2673 ・ Tatsutsugu Matsuzawa, Yasumitsu Aoki, Nobuyoshi Takeuchi, Yoshihiko Murayama, rare earth,
29 (1996) 79-87 ・ Yoshihiko Murayama, Ceramics, 32 (1997) 40-43 ・ Tatsushi Matsuzawa, Yasumitsu Aoki, Nobuyoshi Takeuchi, Yoshihiko Murayama, Electrochemistry and Industrial Physics, 65 (1997) 547-549 ・ Yoshihiko Murayama , Hakaru, 42 (1997) 2-7 ・ T.Nakamura, T.Matsuzawa, CC Rowlands, V.Beltran-Lp
pez, GMSmith and P.C.Riedi, J.Chem.Soc.Faraday Tran
s., 94 (1998) 3009-3012 ・ Kazuhiko Kaiya, Naoyuki Takahashi, Takato Nakamura, Takatsugu Matsuzawa, IEICE Technical Report, EID98-84 (1999) 25-29 ・ K.Kaiya, N.Takahashi, T .Nakamura, T.Matsuzawa, GMS
mith and PCRiedi, J. Lumine., 87-89 (2000) 1073-1075 ・ T.Nakamura, K.Kaiya, N.Takahashi, T.Matsuzawa, CCR
owlands, V.Beltran-Lppez, GMSmith and PCRiedi, J.
Mater.Chem., 10 (2000) 2566-2569

In these research papers,
Only the basic knowledge on the emission characteristics and the mechanism thereof, and further the defect chemistry of rare earths are reported, and the stress emission characteristics, the friction emission characteristics or the mechanical emission characteristics described later are not mentioned at all, and at least During the years from the beginning of development to the announcement by Mr. Xu et al., Which will be described later, it is considered that much attention was focused only on the value as a photoexcited phosphor material.

Of the stress emission phenomenon of Xu and Akiyama et al.
Discovery and a series of research MITI, Kyushu Institute of Industrial Technology, Inorganic composite materials department, Functional ceramics laboratory, http://www.kniri.go.jp/ Xu, Akiyama et al. Center for Technology Research, Basic Materials Research Division, Multifunctional Materials Technology Research Group) ・ http://unit.aist.go.jp/kyushu/multi-func.html is for converting mechanical strain energy directly into light energy. Many studies have been conducted so far on the material systems that can be made. Among them, regarding ZnS: Mn-based materials, there is frictional light emission (= a phenomenon in which light is emitted by applying friction), and the reversible light emission performance thereof is excellent, and the like, and the following papers are announced. In particular, the paper [Appl.Phys.Lett., 74 (1999) 1236-1
[238]], the application to artificial skin using ZnS: Mn film also has a content of expectation (however,
There is no specific description).

CN.Xu, T. Watanabe, M. Akiyama, P. Sun an
d XGZheng, 6th Int'l Symp.Ceram.Mater. & Compo.Eng
ines, (1997) 937-941 ・ CN.Xu, T.Watanabe and M.Akiyama, J.Am.Ceram.Soc.,
82 (1999) 2342-2344 ・ CN.Xu, T.Watanabe, M.Akiyama and XG.Zheng, Appl.P
hys.Lett., 74 (1999) 1236-1238 ・ T.Watanabe, M.Akiyama, CN.Xu, I.Usui and XG.Zhen
g, Adv.Sci. & Tech., 25 (1999) 17-24 [9th Cimtec-World
Forum on New Materials Symposium VIII-Smart Materi
als Systems, P.Vincenzini (Editor)] ・ CN.Xu, T.Watanabe, M.Akiyama and XGZheng, Mater.
Res.Bull., 34 (1999) 1491-1500 ・ CN.Xu, XGZheng, T.Watanabe, M.Akiyama and I.Usu
i, Thin SolidFilms, 352 (1999) 273-277 ・ Chuo Xu, Tadahiko Watanabe, Morito Akiyama, Asahi Zheng, Proceedings of the 7th Intelligent Materials Symposium,
March 19th, 1997, pp.15-17 ・ Xu Zhou Man, Intelligent Materials, Vol.8, No.1 (1998) 20
-25 ・ CN.Xu, Y.Liu, M.Akiyama, O.Agyeman, XGZheng, Ex.Ab
str.1st.Asian Mtg.Electroceramics and 20th Ele.Di
v, Mtg. (Proceedings of the 20th Conference on Electronic Materials Research, 1st Asia Electroceramics Conference), 2PA-11 (2000.10.26-2)
7), p.89

In addition to ZnS: Mn, Sr aluminate-based materials (SrAl ₂ O ₄ : Eu, Sr ₃ Al)
_{For the} first time, we have discovered that ₂ O ₆ : Eu, etc.) have the property of stress luminescence (= a phenomenon that shines when mechanical energy is applied), and have published the following paper.

M.Akiyama, CN.Xu, K.Nonaka and T.Wata
nabe, Appl. Phys. Lett., 73 (1998) 3046-3048 [Sr ₃ Al
₂ O ₆ : Eu, Dy] ・ CN.Xu, T.Watanabe, M.Akiyama and XGZheng, Appl.P
hys.Lett., 74 (1999) 2414-2416 [SrAl ₂ O ₄ : E
u] ・ M.Akiyama, CN.Xu, M.Taira, K.Nonaka and T.Watanab
e, Phil.Mag.Lett., 79 (1999) 735-740 [Sr ₃ Al ₂ O
₆ : Stress emission mechanism of Eu] ・ M.Akiyama, CN.Xu, H.Matsui, K.Nonaka and T.Watanab
e, Appl.Phys.Lett., 75 (1999) 2548-2550 [Ca ₂ Al ₂
SiO ₇ : Ce] ・ CN.Xu, XGZheng, M. Akiyama, K. Nonaka and T. Watana
be, Appl.Phys.Lett., 76 (2000) 179-181 [SrAl ₂ O
₄ : Eu] ・ M.Akiyama, C.Xu, H.Matsui, K.Nonaka and T.Watanabe,
J. Mater. Sci. Lett., 19 (2000) 1163-1165 [Sr ₄ Al ₁₄
O ₂₅ : Eu, Dy stimulated emission] ・ Morito Akiyama, Xuo Xu, Tadahiko Watanabe, Alliance with Light, (19
99.12) p.29-31 ・ Suyo Suh, 35th Anniversary of the foundation ・ Abstracts of the Kyushu Institute of Industrial Technology Research Conference (Aiming to be a development base of composite material technology), 2000.2.16, p.23-28 , Chemical Industry (October 2000 issue) pp.790-794
& 808 ・ Akiyama Morito, Xu Choo, Liu Gei, Matsui Hiroaki, Nonaka Kazuhiro, Watanabe Tadahiko, Proceedings of 13th Autumn Symposium of the Ceramic Society of Japan, (2000) p.102 ・ Xu Choo, Matsui Hiroaki, Akiyama Morito, Liu Gei , Kazuhiro Nonaka, Tadahiko Watanabe, Proceedings of the 13th Autumn Symposium of the Ceramic Society of Japan, (2000) p.132

Further, they also show the results of research on stress luminescence in a system having spinel type ZnAl ₂ O ₄ as a matrix and stress luminescence of a silicate (rare earth doped Y ₂ SiO ₅ system) oxide material. As reported.・ Shuo Xu, Hiroaki Matsui, Morito Akiyama, Liu Gei, Tadahiko Watanabe, Proceedings of 13th Autumn Symposium of the Ceramic Society of Japan, (2000) p.131 ・ H.Matsui, CN.Xu, T.Watanabe and H.Tateyama, Ex.Abs
tr.1st.Asian Mtg.Electroceramics and 20th Ele.Div.
Mtg. (1st Asian Electroceramics Conference 2nd
Proceedings of the 0th Electronic Materials Research Symposium), 2PA-11 (2000.1
0.26-27), p.57 ・ Y.Liu, CN.Xu, H.Matsui, T.Imamura and T.Watanabe,
J. Lumine., 87-89 (2000) 1297-1299

In addition, Xu and Akiyama et al. Reported at the 2000 Ceramic Society of Japan Autumn Symposium that they have investigated the stress emission of the following substance groups so far.
However, there is no mention of which material showed how much stress luminescence. ZnS: Mn, CaAl ₂ O ₄ : Eu, MgAl
₂ O ₄ : Ce, BaAl ₂ O ₄ : Eu, Sr ₂ Al ₃ O
₆ : Eu, ZnAl ₂ O ₄ : Mn, CaAl ₂ Si
O ₇ : Ce, SrMgAl ₁₁₀ O ₁₇ : Eu, Ba ₃ Mg Si ₂ O ₈ : Eu, MgGa ₂ O ₄ : Mn

About Xu and Akiyama Group's patent applications
Furthermore Te, Xu, a group of Akiyama et al., Also patents related to the material system has many filed abroad, are part patent. The publications or registered patents and their brief contents are listed below.

Japanese Patent No. 2754183 (Japanese Patent Laid-Open No. 9-5
No. 4043) A device for electrically connecting a piezoelectric body such as PZT and an electrochromic material such as WO ₃ to monitor a stress state by color change. [Patent Document 1] Japanese Patent Laid-Open No. 10-209503 A method of electrically connecting a piezoelectric body and a light emitting element such as an LED, and converting the light into electricity through electricity generated by external pressure.・ Patent No. 2972859 (Japanese Patent Laid-Open No. 10-259373)
(Patent document) ZnS: Mn is a treatment method for improving the luminous efficiency. Japanese Patent Laid-Open No. 11-116946 discloses wurzite for mechanical energy from the outside.
A material that emits light when received by a piezoelectric material and contains 0.01 to 20 wt% of a rare earth element or a transition metal therein. & JP-A-11-120801 discloses the material patent is a material which emits light by results by adding film version JP 2000-119647 discloses a mechanical external force (JP-A-11-116946 Publication) deformation, MgAl ₂ O ₄ , CaAl ₂ O ₄ , Al ₂ O ₃ ,
The base material of SrMgAl ₁₀ O ₁₇ has 3d, 4d, 5d, 4
A substance containing a transition element or a rare earth element having an electron shell of f and a method for producing the same. Japanese Patent Application Laid-Open No. 11-263970, 3d, 4d, 5 in the host crystal of the metal oxide / composite oxide
A material which emits light by mechanical deformation made of a substance containing a transition element or a rare earth element having an electron shell of d or 4f as an emission center ion. -Patent No. 2958450 (JP-A-11-219601)
Gazette) A method of forming a thin film of an inorganic material which emits light by mechanical external force on a glass surface at a temperature of T _g (glass transition temperature) or lower. -Patent No. 2992631 (Japanese Patent Laid-Open No. 2000-63824)
Gazette) Sr ₃ Al ₂ O ₆ , Ca ₃ Al ₂ O ₆ matrix material containing a transition element or a rare earth element, and the amount of additive substance is 0.01
-20 wt% and baking in a reducing atmosphere at 800 ° C to 1700 ° C. · JP 2000-144129 JP _{MAl 4 O 7 (M = Mg} , Ca, Sr, Ba) was used as a host crystal, activator and Eu, is excited to a transition metal or a rare earth element in the visible light with a co-activator Luminescent phosphor. Japanese Patent Application Laid-Open No. 2000-189805 A phosphorescent aluminate compound (containing rare earth) and a layered / tunnel structure compound (for example, Pt—K ₂ Ti ₆ O ₁₇ ) to which a transition metal element exhibiting catalytic activity is added are mixed. photocatalyst. -Patent No. 3079262 (JP 2000-22621A)
No. 6) LaNiO ₃ transparent conductive thin film with low resistance (almost unrelated to stress emission) -Japanese Patent Laid-Open No. 2000-313878 In a material that converts mechanical energy from the outside into light,
A material in which a Y-Ba-Mg-Si-oxide is used as a base material and a rare earth or a transition metal element is used as a luminescent center. Japanese Patent Laid-Open No. 2001-49251 discloses a mechanically defined aluminate having a non-stoichiometric composition. A material that emits light by energy. Japanese Patent Application Laid-Open No. 2001-64638 Oxide having a melilite type crystal structure (for example, CaYAl ₃
O ₇ , Ca ₂ Al ₂ SiO _7, etc.) as a matrix, a material that emits light by mechanical energy. US Pat. No. 6,117,574 (registered September 12, 2000), which claims a piezo-related material as a triboluminescent material.
-Compatible with two cases, Japanese Patent Laid-Open No. 116946 and Japanese Patent Laid-Open No. 11-120801. US Pat. No. 6,159,394 (December 12, 2000)
Japan registered) Sr ₃ Al ₃ O ₆ is mainly claimed as a stress-stimulated luminescent material, and is disclosed in Japanese Patent No. 2992631 (Japanese Patent Laid-Open No. 2000-
63824).

Recent reports on SrAl ₂ O ₄ -based luminescent materials
In the above, the SrAl ₂ O ₄ -based material was used as a phosphor doped with Eu in the 1960s, and around 1993, SrAl ₂ O ₄ : Eu + by Nemoto Special Chemical Co., Ltd.
Dy's development attracted the spotlight as a long-afterglow phosphor, and around 1997, Xu and Akiyama et al. Revealed that these substances have the ability to emit intense stress. I've explained.

Then, the subsequent research reports on the SrAl ₂ O ₄ type material will be briefly summarized below. ◎ SrAl by Toyo University and Nemoto Special Chemical Co., Ltd.
Study on long afterglow characteristics of ₂ O ₄ : Eu + Dy and CaAl ₂ O ₄ : Eu + Nd single crystals.・ T.Katsumata, T.Nabae, K.Sasajima and T.Matsuzawa,
J. Crystal Growth, 183 (1998) 361-365

◎ Laser-heated pedestal growth by University of Puerto Rico and University of Georgia
growth, LHPG) method of SrAl ₂ O ₄ : Eu + D
y, Growth study of CaAl ₂ O ₄ : Eu + Nd single crystal.・ W.Jia, H.Yuan, L.Lu, H.Liu and WMYen, J.Lumine., 76
& 77 (1998) 424-428 ・ W.Jia, H.Yuan, L.Lu, H.Liu and WMYen, J.Crystal Gr
owth, 200 (1999) 179-184 ・ W.Jia, H.Yuan, S.Holmstrom, H.Liu and WMYen, J.Lum
ine., 83-84 (1999) 465-469

◎ Long afterglow characteristics in single crystal SrAl ₂ O ₄ : Eu + Dy. Huabiao.Yuan, "The Investigation of Long Persiste"
nt Afterglow in SrAl ₂ O: Eu, Dy Single Crystal "Dissertation submitted to The University of Georgi
a, (Sept. 1998)

◎ Long afterglow SrAl ₂ by Institute of Molecular Science
Excitation spectrum study of O ₄ : Eu + Dy ・ M.Kamada, J. Murakami and N. Ohno, J. Lumine., 87-89
(2000) 1042-1044 ◎ Solid solution type (Sr, Ca) Al ₂ by Korean research institute
O _4: light-emitting research · SHJu for Eu, SGKim, JCChoi, HLPark, S.-I.Mho and T.
W. Kim, Mat. Res. Bull., 34 (1999) 1905-1909

Single crystal by the floating zone method by Toyo University: SrAl ₂ O ₄ , SrAl ₄ O ₇ , Sr ₃ Al ₂ O ₆ ,
Study on emission characteristics of SrAl ₁₂ O ₁₉ .・ T.Katsumata, K.Sasajima, T.Nabae, S.Komuro and T.Mo
rikawa, J. Am. Ceram. Soc., 81 (1998) 413-416

◎ SrAl ₂ O ₄ : Eu by sol-gel method
+ Dy and boron addition effect ・ IC.Chen and TM.Chen, J.Mater.Res., 16 (2001) 644-6
51 ◎ Characteristics of Pb ²⁺ ion in various Sr-aluminates ・ CPJoshi and SVMoharii, Phys.Stat.Sol. (B), 220
(2000) 985-989

◎ Long afterglow characteristic of Eu, Dy co-doped Sr-Al-oxide phosphor.・ Hisako Takahashi, Sethkyu Tabe, Sadakazu Hanada, J.Ceram.Soc.Japa
n, 104 (1996) 322-326 ◎ Long afterglow photoconductivity of SrAl ₂ O ₄ : Eu, Dy single crystal.・ HBYuan, W.Jia, SABasun, L.Lu, RSMeltzer and W.
M. Yen, J. Electrochemi. Soc., 147 (2000) 3154-3156

◎ Plasma display panel (PD
SrAl ₂ O ₄ : Eu as a green phosphor for P)
Evaluation (Tottori University and NEC Corporation) ・ M.Ashida, K.Okamoto, I.Ozaki, H.Fukuda, K.Ohmi, S.Tan
aka, H.Kobayashi, M.Hayashi and M.Minamoto, IDW '98 (P
roc.5th Int.Display Workshops (1998) 597-600 ◎ A simple column on phosphorescent materials. It also mentions mixing with plastic. (Tohoku University) ・ Tadao Endo, Synthetic Resin, 43 (1997) 10

SrAl ₂ O ₄ : Flux effect / particle size effect on afterglow characteristics of Eu powder. (Kyushu University) ・ Keiko Tanaka, Takahiro Murata, Kenji Morinaga, Resources and Materials, 114 (19
98) 965-969 ◎ SrAl ₂ O ₄ film was formed on the stainless steel (SUS304) substrate by laser spraying method and the thermoluminescence property was discussed.・ Joe Horie, Koki Sato, Eiji Inoue, Proceedings of the Japan Society for the Shooting Society National Conference, 62 (1995) 38-39

◎ (Ba, Sr) Al ₂ O ₄ : Eu fluorescence characteristics.・ SHMPoort, WP Blokpoel and G.Blasse, Chem.Mate
r., 7 (1998) 1547-1551 ◎ (MgSr) Al ₂ O ₄ : Eu and (MgBa) A
l ₂ O ₄ : Eu emission characteristics ・ X.Zhang, Y.Zhai and S.Wu, Huagong Yejin (Engin.Che
m. Metallugy), 19 (1998) 109-112

⊚ Crystallinity and long afterglow characteristics of SrAl ₂ O ₄ : Eu and thermoluminescence.・ Tang Ming Road, Lee Chang-Han, Takashi Takeshi, Xu Xiao Hong, Xue Xue, Cai Kun, Ch
inese J. Luminescence, 16 (1995) 51-56 ◎ SrAl ₂ O ₄ : E via monitoring emission.
Analysis of high temperature solid state reaction of u.・ YKSong, SKChoi, HSMoon, TWKim, S.-I.Mho and
HLPark, Mater.Res.Bull., 32 (1997) 337-341 ◎ SrAl ₂ O ₄ : Hydrothermal synthesis of Eu fine particles ・ TRNKutty, R. Jagannathan and RPRao, Mater.Res.
Bull., 25 (1990) 1355-1362

◎ Explanation of optical properties of rare earth aluminate-based phosphorescent phosphors such as SrAl ₂ O ₄・ Setsuhisa Tabe, Sadakazu Hanada, New Ceramics, Vol.9
, No.10 (1996) 27-33 ◎ SrAl ₂ O prepared from wet type
₄ : Fluorescence characteristics of Eu particles ・ Z.Zhang, Z.Feng, Y.Lin and Z.Tang, Ann.Mtg.Ceram.So
c.Japan, 2 C 10 (1996) 65

◎ Fluorescent properties of acicular fine particles SrAl ₂ O ₄ : Eu ・ Z.Zhongtai, L.Yuanhua, T.Zilong, Z.Feng and H.Chuan
yong, Ann.Mtg.Ceram.Soc.Japan, 1 G 12 (2000) 65 ◎ SrAl ₂ O ₄ prepared by gel method: Fluorescence characteristics of Eu particles ・ Z.Tang, F.Zhang, Z.Zhang, C .Huang and Y.Lin, J.Euro.
Ceram.Soc., 20 (2000) 2129-2132

◎ 3 doped in SrAl ₂ O ₄ matrix
Characteristics of highly charged V ions S. Kuck and P. Jander, Chem. Phys. Lett., 300 (1999) 189
-194 ◎ A series of research on SrAl ₂ O ₄ : Eu thin film materials by Niigata University ・ Tatsumi Denai, Hidehiko Shimizu, Takahiro Kawakami, Kazunari Shinbo, Keizo Kato,
Kaneko Futoshi, Ota Masatoshi, IEICE Technical Report (Technical Review), CPM-95-62 (1995) 13-18 ・ Matsui Tatsu, Uemura Takuya, Kawakami Takahiro, Shinbo Kazunari, Kato Kage three,
Kaneko, F., Ota, M., IEICE Technical Report (Technical Report), CPM-97-60 (1997) 55-60 ・ Matsui Tatsu, Uemura Takuya, Ogura Yukihiro, Kato Keizo, Shinpo Issei,
Futao Kaneko, Masatoshi Ota, Takahiro Kawakami, IEICE Technical Report (Technical Report), CPM-98-113 (1998) 1-6 ・ Tatsumi Denai, Takuya Uemura, Keizo Kato, Futoshi Kaneko Man, Kazunari Shinbo,
Masatoshi Ota, Takahiro Kawakami, Transactions of the Institute of Electrical Engineers of Japan, 118-A (1998) 101
5-1020 ・ K.Kato, I.Tsutai, T.Kamimura, F.Kaneko, K.Shinbo, MO
hta and T.Kawakami, J.Lumin., 82 (1999) 213-220 ・ I.Tsutai, T.Kamimura, K.Kato, F.Kaneko, K.Shinbo, MO
hta and T. Kawakami, Proc. 1998 Int'l Symp. Elect. Insu
l.Mater. & 1998 AsianInt'l Conf.Diele.Elect.Insul.
& 30th Symp.Elect.Insul.Mater. (Symposium on Electrical Insulation Materials)., (1998) 51-54 ・ Masato Ota, Yoki Hayakawa, Mizuho Maruyama, Tomohiko Saijo, Rare Earths, 32 (1998) 142-143 ・Junichi Miyoshi, Daisuke Oki, Kenji Toda, Mineo Sato, Rare Earth, 34
(1999) 266-267 ・ Masato Ota, Mizuho Maruyama, Tomohiko Saijo, Rare Earths, 36 (2000)
244-245 ・ Masato Ota, Haruki Hayakawa, Mizuho Maruyama, Tomohiko Saijo, No. 11
Proceedings of the Autumn Meeting of the Ceramic Society of Japan,
1 C 02 (1998) 45 ・ M.Sengiku, Y.Oda, W.Jiang, K.Yatsui, Y.Ogura, K.Kato,
K. Shinbo and F. Kaneko, Jpn. J. Appl. Phys., 40 (2001) 103
5-1037 ・ K.Kato, Y.Ogura, M.Sengiku, K.Shinbo, F.Kaneko, Y.Oda
and K. Yatsui, Jpn.J.Appl.Phys., 40 (2001) 1038-1041

◎ Research on trap level and mechanism of thin film and rare earth ions in Nakazawa laboratory of Kogakuin University ・ Eiichiro Nakazawa, Toshiki Mochida, Jun Oka, Proceedings of the Society of Physics, 258 (1995) 25-34 ・Toshiki Mochida, Kenichi Kamiyama, Eiichiro Nakazawa, Kogakuin University Research Report, No.81 (1996) 83-90 ・ E.Nakazawa and T.Mochida, J.Luminescence, 72-74 (19
97) 236-237 ・ Kota Yonezawa, Eiichiro Nakazawa, Yoshinori Murasaki, Kogakuin University Research Report, No.86 (1999) 153-159

Report Cases of Other Related Light-Emitting Materials Further, referring to report cases in which the composition of aluminate is variously changed, a paper relating to a SrAl ₁₂ O ₁₉ -based light-emitting material is published as follows. .・ EFRiebling, Mat.Res.Bull., 10 (1975) 997-1004 ・ J.Huang, H.Wang, J.Hu and X.Yu, J.Lumin., 40 & 41 (198
8) 157-158 ・ HTHintzen, CJMDenissen and HMvan Noort, Ma
t.Res.Bull., 24 (1989) 247-259 ・ LD Merkle, B.Zandi, R.Moncorge, Y.Guyot, HRVerdun
and B.Mcintosh, J.Appl.Phys., 79 (1996) 1849-1856 ・ B.Zandi, LDMerkle, JBGruber, DEWortman and C.
A. Morrison, J. Appl. Phys., 81 (1997) 1047-1054 ・ AMSrivastava and WWBeers, J. Lumin., 71 (1997) 28
5-290 ・ HRVerdun, DEWortman, CAMorrison and JLBrad
shaw, Opt.Mater., 7 (1997) 117-128 ・ SRJansen, HTHintzen, R.Metselaar, JWde Haan,
LJMvan de Ven, APMKentgens and GHNachtegaa
l, J.Phys.Chem.B, 102 (1998) 5969-5976 ・ S.Maschio, E.Lucchuni and V.Sergo, J.Am.Ceram.So
c., 82 (1999) 3145-3149 ・ JSChoi, SHBaek, SGKim, SHLee, HLPark, S.-I.
Mho, TWKim and YHHwang, Mat.Res.Bull., 34 (1999) 55
1-556

Further, other aluminate phosphors (Sr
₂ Al ₆ O ₁₁ : Eu, Sr ₄ Al ₁₄ O ₂₅ : Eu, BaA
There are also reported examples of 1 ₂ Si ₂ O ₈ and SrAl ₂ Si ₂ O ₈ ).・ D.Wang and M.Wang, J. Mater.Sci. Lett., 18 (1999) 1433
-1435 ・ Keiji Ichinomiya, Kiyotaka Arai, Hiroto Tamaki, Yoshinori Murasaki, Tomohiro Oishi, Proceedings of Physics Society of Japan, 270 (1998) 9-16 ・ K.Tanaka, T.Ishihara, K.Fujita and K. Hirano, Mater.
Res.Soc.Symp.Proc., 604 (2000) 323-328T.Ishihara, K.Tanaka, K.Fujita, K.Hirao and N.Soga,
Solid State Communi., 107 (1998) 763-767

There is also an example of an investigation report on triboluminescence of a substance obtained by doping ZnO with trivalent rare earth ions.・ JC Ranfard-Haret, P.Valat, V.Wintgens and J.Kossa
nyi, J. Lumine., 91 (2000) 71-77

On the other hand, not only the above-mentioned inorganic compounds but also the mechanoluminescence of molecular crystals and organic materials have been reported.・ BPChandra, Mol.Cryst.Liq.Cryst., 142 (1987) 157-17
2 ・ BPChandra, MSKhan and MHAnsari, Cryst.Res.Te
chnol., 33 (1998) 291-302 ・ GT Reynolds, J. Lumine., 75 (1997) 295-299

Particularly recently, there have been many reports on mechanoluminescence of Eu complex.・ N.Takada, J. Sugiyama, R. Katoh, N. Minami and S. Hied
a, Synthetic Metals, 91 (1997) 351-354 ・ N.Takada, S.Hieda, J.Sugiyama, R.Katoh and N.Minam
i, Synthetic Metals, 111-112 (2000) 587-590 ・ XF.Chen, SH.Liu, CY.Duan, YH.Xu, XZ.You, J.Ma an
d NB.Min, Polyhedron, 17 (1998) 1883-1889 ・ XR.Zeng, RG.Xiong, XZ.You and KK.Cheung, Inorg.
Chem.Commun., 3 (2000) 341-344 ・ Tokuda Takayuki, Kobun, Vol. 48, March (1999) 143 However, the emission of these molecular crystals and Eu complex is higher than that of the above inorganic materials. Low, from the current perspective, it cannot be said to be of high industrial importance.

In addition, as an additional publicly known document related to the present invention, a research example of a phenomenon of emitting light upon destruction of a solid, G. Alzetta, I. Chudacheck and R. Scarmozzino, Phys. St.
at.Sol. (a), 1 (1970) 775-785, and a case study of a phenomenon that emits light during an earthquakeJSDerr, Bull.Seismological Soc.Amer., 63 (1973) 21
77-2187 and a study example of a phenomenon (triboluminescence) that emits light during friction that is closely related to stress emission, AJ Walton, Adv. Phys., 26 (1977) 887-948, etc. are already known. However, although some kind of mechanical connection can be imagined between the phenomenon of emission of light during an earthquake and destructive emission, the relationship with stress emission is still unclear. Furthermore, regarding the difference between frictional luminescence and stress luminescence, which is also being investigated in detail, the relationship is not always clarified.

[0041]

According to the knowledge of the present inventor, the situation that has been clarified so far can be summarized as follows. 1. SrA as a phosphor material that has been known for a long time
l ₂ O ₄ : Eu material 2. Long persistence phosphor SrAl ₂ by Nemoto Special Chemical Co., Ltd.
Presence of O ₄ : Eu + Dy material However, stress luminescence is not mentioned. 3. Existence of composite material of the above phosphor and resin by Nemoto Special Chemical Co., Ltd. 4. SrAl ₂ by Xu and Akiyama et al. At the Kyushu Institute of Industrial Technology
Discovery of stress emission phenomenon due to O ₄ : Eu material 5. SrAl ₂ by Xu and Akiyama et al. At the Kyushu Institute of Industrial Technology
O ₄ : Experiment and confirmation of stress emission phenomenon by compounding Eu material and resin

By the way, a product name "Luminova" (SrAl ₂ O ₄ :
Eu + Dy) resin-impregnated product is "kneaded resin pellet"
Is sold as follows.・ Http://www.nemoto.co.jp/products/luminova/index.
html ・ http://www.nemoto.co.jp/products/gss/index.html

As the resin material, polymethylmethacrylate (PMMA), ABS resin, polycarbonate (P
C), polystyrene (PS), polyethylene (PE),
Polypropylene (PP), polyacetal (PA), and urethane resins are available on the web and papers [Measuring, vol.42 (199
7) 2.]. Furthermore, according to the above-mentioned Web material, it seems that kneading into silicone rubber is also being attempted. On the other hand, it is described that the mixing ratio of the powder and the resin is about 10% by weight.

However, since the above composite material or sheet-shaped molded product is very hard, it cannot be easily bent by human power, and as a result, it is difficult to easily perform stress emission. Furthermore, since the above resin kneaded material originally has a long afterglow property, it seems that it always emits light, and it does not look like it glows only when touched, so it is used, for example, as a member for entertainment. There is a difficulty in doing so.

The present invention aims to solve these problems. That is, the problem to be solved by the present invention is to provide a fluorescent substance, a composite material, and a light emitting device using these, which can easily cause stress luminescence even by human power. Another problem to be solved by the present invention is to provide a fluorescent substance, a composite material, and a light emitting device using these, which can cause stress emission when touched. Still another problem to be solved by the present invention is to provide a fluorescent substance, a composite material, and a light emitting device using these, which can easily control stress emission by a signal from the outside. The above and other objects of the invention will be apparent from the description of the present specification.

[0046]

The inventor of the present invention has made extensive studies in order to solve the above problems of the prior art. The outline is as follows. As mentioned above, the following two points are important issues. 1. 1. Make the composite material flexible 2. 2. When a person touches it lightly, it shines, and in order to clearly see the situation, the ratio of the amount of light emission when pressure is applied is set to be as large as possible. When an electric signal from the outside is received, for example, an electric signal is given to the piezoelectric material to excite the piezoelectric vibration, and the stress-stimulated luminescent material at a specific site affected by the vibration vibrates to emit light.

In order to satisfy these requirements, for example, 1. 1. Use SrAl ₂ O ₄ : Eu or the like that does not exhibit long afterglow (naturally, SrAl ₂ O ₄ : Eu emits stress). In compounding with a resin or the like, the filling rate is further increased to 30% or more and less than 100%, preferably 30% or more and 80% or less, and a thin sheet is formed. It is effective that the above-mentioned sheets are arranged at appropriate intervals on the two-dimensional surface so that the stress-stimulated luminescent material in a specific portion vibrates in response to an electric signal from the outside.

By the way, as will be described in detail later, the present inventors have made a detailed study on the phenomenon that light emission occurs when a force is applied to a substance such as SrAl ₂ O ₄ : Eu. It was found that the light emission can be controlled by changing with time, and specifically, the on / off of the light emission or the control of the light emission intensity can be controlled. That is, in order to cause light emission or change the light emission intensity, it is not important to simply generate stress, but it is particularly important to give a time change rate of stress.

The present invention was devised as a result of further various investigations based on the above investigations and findings. That is, in order to solve the above-mentioned problems, the first invention of the present invention is a fluorescent substance, which emits light depending on the rate of change of stress with time. Here, the rate of change of stress with time is dσ / d, where σ is stress and t is time.
It can be represented as t. The stress includes thermal stress as well as mechanical stress.

A second aspect of the present invention is a fluorescent substance characterized in that the emission intensity changes depending on the rate of change of stress with time. The rate of change of stress with time can be translated into the rate of application or release of external force.

That is, the third aspect of the present invention is a fluorescent substance which emits light depending on the rate of application or release of external force. A fourth invention of the present invention is a fluorescent substance characterized in that the emission intensity changes depending on the rate of application or release of an external force.

A fifth aspect of the present invention is a composite material which emits light depending on the rate of change of stress with time. A sixth aspect of the present invention is a composite material, wherein the emission intensity changes depending on the rate of change of stress with time.

A seventh aspect of the present invention is a composite material which emits light depending on the rate of application or release of external force. An eighth invention of the present invention is a composite material, wherein the emission intensity changes depending on the speed of application or release of external force.

The ninth invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light depending on the rate of change of stress with time. 10th of this invention
The invention of 1) is a composite material comprising a fluorescent substance and another substance, wherein the emission intensity changes depending on the time change rate of stress.

The eleventh invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light depending on the rate of application or release of an external force. A twelfth invention of the present invention is a composite material comprising a fluorescent substance and another substance, wherein the emission intensity changes depending on the rate of application or release of an external force.

The thirteenth invention of the present invention is a fluorescent substance, which emits light only by touching it with a hand. A fourteenth invention of the present invention is a composite material, which emits light only by touching with a hand. Here, when light is emitted only by touching it with a hand, this includes not only the case where a time change rate of stress is obtained but also the case where a constant force is applied for a certain time and a displacement of a certain distance occurs.

A fifteenth invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light only by touching with a hand. The sixteenth invention of this invention is
It is a fluorescent substance that emits light by causing elastic vibration.

The seventeenth invention of the present invention is a composite material which emits light by causing elastic vibration. An eighteenth invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light when elastic vibration is caused. To cause the above elastic vibration, it is effective to apply a sound wave, particularly an ultrasonic wave.

That is, the nineteenth invention of the present invention is a fluorescent substance which emits light when a sound wave is applied. A twentieth invention of the present invention is a composite material which emits light when a sound wave is applied.

The twenty-first invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light when a sound wave is applied. A twenty-second aspect of the present invention is a fluorescent substance, which emits light when exposed to ultrasonic waves.

The twenty-third invention of the present invention is a composite material which emits light by applying ultrasonic waves. A twenty-fourth invention of the present invention is a composite material comprising a fluorescent substance and another substance, which emits light when exposed to ultrasonic waves.

The other substance used together with the fluorescent substance in the above composite material can be appropriately selected according to the application etc., and may be one kind or two or more kinds. Any inorganic material may be used, but from the viewpoint of providing flexibility, an elastic body is preferably used. In this case, the weight ratio of the fluorescent substance is preferably 30% or more and less than 100%, more preferably 30% or more and 80% or more.
% Or less. Young's modulus of the elastic body is typically 10M
Pa or higher. The elastic body is typically an organic material, and specifically, for example, polymethylmethacrylate (PMMA), ABS resin, polycarbonate (P
C), polystyrene (PS), polyethylene (PE),
It is composed of at least one material selected from the group consisting of polypropylene (PP), polyacetal (PA), urethane resin, polyester, epoxy resin, silicone rubber, an organic silicon compound having a siloxane bond, and an organic piezoelectric material. Here, examples of the organic piezoelectric material include polyvinylidene fluoride (PVDF) and polytrifluoroethylene copolymer. In addition, examples of the inorganic substance-based elastic body include inorganic glass.

In the present invention, the fluorescent substance is typically an oxide containing aluminum, gallium or zinc as one of the constituent elements, more specifically, an alkaline earth metal and an oxide of aluminum, gallium or zinc. A substance is used as a base, and this is doped with a rare earth element.
Here, one kind or two or more kinds of rare earth elements are doped depending on the application. A typical example of the case where only one kind of rare earth element is doped is the case where Eu is doped, and it is suitable for an application requiring a short afterglow. A specific example of such a fluorescent substance is SrAl ₂ O ₄ : Eu. Also,
A specific example of the composite material is that the fluorescent substance is SrAl ₂ O ₄ : E.
u, and the elastic body as another substance is polyester, acrylic resin, or a mixture thereof. A typical example when two or more rare earth elements are doped is Eu.
This is a case where both Dy and Dy are doped, which is suitable for applications in which long afterglow is positively utilized. The fluorescent substance may be, for example, ZnS: Mn, ZnS: Ti, Zn doped with manganese and / or titanium in addition to an oxide containing aluminum, gallium or zinc as one of the constituent elements.
It may be S: Mn, Ti, or the like.

The fluorescent substance or the composite material is prepared in a shape and a size according to the intended use. For example, in the case of a sheet-like shape, its thickness is preferably 1 mm or less, more preferably 0.5 mm or less from the viewpoint of ensuring flexibility. Further, in the case of a fibrous or fibrous shape, the thickness thereof is preferably 1 mm or less, and more preferably 0.5 mm or less from the viewpoint of ensuring flexibility. Furthermore,
From the viewpoint of ensuring the flexibility of the fluorescent substance or the composite material, the shape of the fluorescent substance itself is, for example, a fiber shape,
The shape may be sponge-like or network-like.

The fluorescent substance is aluminum as a constituent element,
It may contain gallium or zinc, as well as aluminum and silicon, for example. In one form, the fluorescent substance is composed of fine particles having a diameter of 100 nm or less and is crystalline. In the composite material including the crystalline fluorescent substance and the elastic body, the elastic body is typically amorphous. Depending on the application, the composite material may be gelled as a whole.

The composite material can be manufactured by various methods. In particular, the following method is used for manufacturing a composite material composed of a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body. Is effective. That is, a twenty-fifth invention of the present invention is a method for producing a composite material, which comprises a fluorescent substance made of fine particles having a diameter of 100 nm or less and an elastic body, and emits light depending on a time change rate of stress. It is characterized by using a dehydration / condensation reaction of a siloxane compound and a metal alkoxide.

The twenty-sixth aspect of the present invention has a diameter of 100.
A method for producing a composite material comprising a fluorescent substance composed of fine particles of nm or less and an elastic body, the emission intensity of which changes depending on the time rate of change of stress, which is a dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. It is characterized by using.

The twenty-seventh invention of the present invention has a diameter of 100.
A method for producing a composite material comprising a fluorescent substance composed of fine particles of nm or less and an elastic body, which emits light depending on the rate of application or release of an external force, which comprises dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. It is characterized by being used.

The twenty-eighth invention of the present invention has a diameter of 100.
A method for producing a composite material comprising a fluorescent substance composed of fine particles of nm or less and an elastic body, the emission intensity of which changes depending on the rate of application or release of an external force, which comprises dehydration of a polysiloxane compound and a metal alkoxide. It is characterized by using a condensation reaction.

The twenty-ninth invention of the present invention has a diameter of 100
A method for producing a composite material, which comprises a fluorescent substance composed of fine particles of nm or less and an elastic body and emits light only by touching with a hand, characterized by using a dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. It is a thing.

The thirtieth invention of the present invention has a diameter of 100.
A method for producing a composite material comprising a fluorescent substance composed of fine particles of nm or less and an elastic body, which emits light by causing elastic vibration, characterized by using a dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. It is what

The thirty-first invention of the present invention has a diameter of 100.
A method for producing a composite material, which comprises a fluorescent substance made of fine particles of nm or less and an elastic body, and emits light by applying a sound wave, characterized by using a dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. It is a thing.

The thirty-second invention of the present invention has a diameter of 100.
A method for producing a composite material comprising a fluorescent substance composed of fine particles of nm or less and an elastic body, which emits light when exposed to ultrasonic waves, characterized by using a dehydration / condensation reaction of a polysiloxane compound and a metal alkoxide. To do.

In the present invention, as the other substance used together with the fluorescent substance in the composite material, an organic conductive substance which takes in ions and deforms can be used. Examples of such an organic conductive substance include a heteroaromatic ring-type conductive polymer, specifically, polypyrrole, polythiophene, polyaniline and the like. Further, a polymer gel material can be used as another substance. This polymer gel material is, for example, a water-soluble non-electrolyte polymer gel having a heat displacement function, an electrolyte polymer gel that is displaced by pH, a combination of a polymer compound that is electrically displaced and a surfactant, polyvinyl alcohol. It is at least one kind of material selected from the group consisting of a base material and a polypyrrole material. Here, the water-soluble non-electrolyte polymer gel having a heat displacement function is, for example, polyvinyl methyl ether or poly-N-isopropylacrylamide, and the electrolyte polymer gel whose displacement is caused by pH is, for example, polyacrylonitrile, which is electrically displaced. The polymer compound is, for example, polyacrylamido-2-methylpropanesulfonic acid.

The fluorescent substance according to the present invention can also be used in coating materials, paints, inks, artificial skin, artificial luminescent skin, artificial luminescent hair, luminescent elements, etc., and if necessary, in combination with other substances. It may be used as a composite material. That is, a thirty-third invention of the present invention is a coating material containing a fluorescent substance which emits light depending on a time change rate of stress. A thirty-fourth aspect of the present invention is a coating material containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time.

A thirty-fifth aspect of the present invention is a coating material containing a fluorescent substance which emits light depending on the rate of change of stress with time. A thirty-sixth aspect of the present invention is a coating material containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time.

The thirty-seventh aspect of the present invention is an ink containing a fluorescent substance which emits light depending on the rate of change of stress with time. A thirty-eighth invention of the present invention is an ink containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time.

The thirty-ninth invention of the present invention is an artificial skin containing a fluorescent substance which emits light depending on the rate of change of stress with time. The 40th invention of this invention is
The artificial skin is characterized by containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time.

A forty-first invention of the present invention is directed to a skin layer made of an artificial skin material, a plurality of optical fibers penetrating the skin layer in a predetermined arrangement, and one end of the optical fiber on one surface side of the skin layer. A fluorescent substance that emits light depending on the rate of change of stress over time, or a composite material consisting of a fluorescent substance and another substance that emits light depending on the rate of change over time of stress. Is an artificial skin characterized by.

A forty-second aspect of the present invention is directed to a skin layer made of an artificial skin material, a plurality of optical fibers penetrating the skin layer in a predetermined arrangement, and one end of the optical fiber on one side of the skin layer. An artificial material having a fluorescent substance that emits light depending on the time change rate of stress, or a composite material that is composed of a fluorescent substance and another substance and that emits light depending on the time change rate of stress. A method of contact information processing of skin, wherein when one surface of artificial skin is in contact with another object,
It is characterized in that the contact information of the object is obtained from the position of the optical fiber where the light is emitted from the other end of the plurality of optical fibers and / or the intensity of the emitted light.

In the 41st and 42nd aspects of the present invention, typically, a plurality of optical fibers are provided in a two-dimensional array on the skin layer. The thickness and spacing of these optical fibers are determined according to the function of the artificial skin. As the artificial skin material, for example, resin is used.

The forty-third invention of the present invention provides a fluorescent substance or a fluorescent substance and other substances having a fibrous or fibrous shape with a thickness of 1 mm or less, which emits light depending on the rate of change of stress with time. An artificial luminescent skin, characterized in that a composite material comprising a substance is implanted in the artificial skin.

A forty-fourth aspect of the present invention is a fluorescent substance or a fluorescent substance and other substances having a fibrous or fibrous shape with a thickness of 1 mm or less, which emits light depending on the rate of change of stress with time. An artificial luminescent hair characterized by using a composite material comprising a substance. These artificial luminescent skin and artificial luminescent hair can be provided, for example, on the surface of the body of entertainment robots or various products.

A forty-fifth aspect of the present invention is a fluorescent substance or a fluorescent substance and other substances having a fibrous or fibrous shape with a thickness of 1 mm or less, which emits light depending on the rate of change of stress with time. A method for producing artificial light-emitting hair using a composite material including a substance, comprising a tube containing a liquid containing fine particles of a fluorescent substance or a liquid containing fine particles of a fluorescent substance and another substance in a liquid state. It is characterized in that one end is inserted, suction is performed from the other end to fill the tube with the liquid, and then the liquid filled in the tube is solidified.

The forty-sixth aspect of the present invention provides a fluorescent substance or a fluorescent substance and other substances having a fibrous or fibrous shape with a thickness of 1 mm or less, which emits light depending on the rate of change of stress with time. A method for producing artificial light-emitting hair using a composite material containing a substance, which is an electrodeposition coating liquid containing fine particles containing a fluorescent substance or an electrodeposition coating containing fine particles containing a fluorescent substance and a raw material of another substance. It is characterized in that a conductive core wire is immersed in a liquid, and fine particles of the fluorescent substance or fine particles of the fluorescent substance and another substance are attached to the surface of the core wire by an electrophoretic method.

A forty-seventh aspect of the present invention is a light-emitting element characterized by using a fluorescent substance which emits light depending on the rate of change of stress with time. The forty-eighth invention of the present invention is a light-emitting device characterized by using a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time.

When a composite material is used for the light emitting element, in order to generate elastic vibration in the composite material and thereby obtain the rate of change of stress with time, for example, a piezoelectric vibrator, a piezoelectric material, or a surface acoustic wave element can be used. . That is, a forty-ninth invention of the present invention is a light-emitting device comprising a piezoelectric vibrator and a fluorescent substance which is joined to the piezoelectric vibrator and emits light depending on piezoelectric vibration.

A fiftieth invention of the present invention comprises a piezoelectric vibrator and a composite material, which is joined to the piezoelectric vibrator, is made of a fluorescent substance and another substance, and emits light depending on the piezoelectric vibration. It is a characteristic light emitting element.

The fifty-first invention of the present invention comprises a piezoelectric vibrator, a fluorescent substance and another substance bonded to the piezoelectric vibrator, and the emission intensity depends on the amplitude and / or frequency of the piezoelectric vibration. A light-emitting element having a composite material that changes. Here, the frequency of the piezoelectric vibration is
Frequencies near the resonance frequency are included.

The fifty-second invention of the present invention is characterized by comprising a surface acoustic wave element and a fluorescent substance which is joined to the surface acoustic wave element and emits light depending on the amplitude and / or frequency of elastic vibration. It is a light emitting element.

The fifty-third invention of the present invention comprises a surface acoustic wave element, a fluorescent substance and another substance bonded to the surface acoustic wave element, and emits light depending on the amplitude and / or frequency of elastic vibration. And a composite material for producing a light emitting device.

The fifty-fourth invention of the present invention comprises a surface acoustic wave element, a fluorescent substance and another substance bonded to the surface acoustic wave element, and emits light depending on the amplitude and / or frequency of elastic vibration. A light-emitting element having a composite material whose intensity changes.

A fifty-fifth aspect of the present invention is a light emitting device having a structure in which a thin film made of a piezoelectric material and a thin film made of a fluorescent substance that emits light depending on piezoelectric vibration are laminated. . A fifty-sixth invention of the present invention comprises a thin film made of a piezoelectric material, a fluorescent substance and another substance,
It is a light emitting element having a structure in which a thin film made of a composite material that emits light depending on piezoelectric vibration is laminated.

A fifty-seventh aspect of the present invention is one in which a thin film made of a piezoelectric material and a thin film made of a composite material which is made of a fluorescent substance and another substance and whose emission intensity changes depending on piezoelectric vibration are laminated. It is a light emitting device having a different structure.

In the fifty-fifth aspect of the present invention, from the viewpoint of obtaining good crystallinity, a thin film made of a piezoelectric material and a thin film made of a fluorescent substance are preferably laminated epitaxially in lattice matching. The 55th to 5th aspects of the present invention
In the invention of Item 7, in order to generate piezoelectric vibration in a thin film made of a piezoelectric material, for example, a pair of electrodes facing each other with a thin film made of a piezoelectric material sandwiched therebetween, or one surface of the thin film made of a piezoelectric material is provided. A pair of comb-shaped electrodes facing each other is provided, and an electric signal is input to these electrodes. When a pair of comb-shaped electrodes facing each other is provided on one surface of a thin film made of a piezoelectric material like the latter, a transistor for light emission control, for example, a MIS transistor is provided, and the drain of this MIS transistor and the pair of comb-shaped electrodes are provided. By electrically connecting one to the other, light emission can be controlled by the on / off operation of the transistor. This light emitting device can be used as one unit of an active matrix device.

The thin film made of the above-mentioned piezoelectric material can be formed on various substrates, but the Si substrate is particularly preferable because it is inexpensive and easily available. When this Si substrate is used, a CeO ₂ thin film is first grown on the Si substrate, and then a thin film made of a piezoelectric material is grown thereon,
It is possible to make an epitaxial lattice match with the CeO ₂ thin film.

In the present invention, a piezoelectric material may be used as another substance used together with the fluorescent substance in the composite material. In this case, in one typical example, the composite material is composed of a grain portion and a grain boundary portion, the grain portion mainly consisting of a piezoelectric material, and the grain boundary portion mainly consisting of a fluorescent substance. The following light emitting device can be formed by using such a composite material.

That is, the fifty-eighth invention of the present invention is a light-emitting element using a composite material which is mainly composed of a fluorescent substance and a piezoelectric material and emits light depending on a time change rate of stress. It is composed of grain part and grain boundary part, particle part is mainly made of piezoelectric material, grain boundary part is mainly made of fluorescent substance, and electrostriction is induced in the composite material by the input of an electric signal from the outside. Is characterized in that an electrode is provided so that light emission can be obtained from the fluorescent material in the grain boundary portion.

The fifty-ninth invention of the present invention is a light-emitting element using a composite material which is mainly composed of a fluorescent substance and a piezoelectric material and whose emission intensity changes depending on the rate of change of stress with time. Is composed of a grain portion and a grain boundary portion, the grain portion is mainly composed of a piezoelectric material, the grain boundary portion is mainly composed of a fluorescent substance, and an electrostriction is induced in the composite material by input of an electric signal from the outside. As a result, the electrode is provided so that light emission can be obtained from the fluorescent substance in the grain boundary portion.

Various materials can be used as the piezoelectric material, but a material having an ABO ₃ type perovskite-related crystal structure is typically used, and specifically, Pb is used.
TiO ₃ based material, PbZrO ₃ based material, Pb (ZrT
i) O ₃ based material, Pb (ZnNb) O ₃ based material and P
At least one material selected from the group consisting of b (MgNb) O ₃ -based materials or a solid solution material thereof is used. As an example of a typical combination of a piezoelectric material and a fluorescent substance, when the piezoelectric material is a Pb (ZrTi) O ₃ -based material and the fluorescent substance is SrAl ₂ O ₄ : Eu, or when the piezoelectric material is This is a case where the fluorescent substance is a Pb (ZrTi) O ₃ system material and the fluorescent substance is SrAl ₂ O ₄ : Eu.

In the present invention, the fluorescent substance is typically an aluminate glass phase containing a rare earth element, and more specifically, a glass phase containing SrAl ₂ O ₄ : Eu fine particles. When the composite material is mainly composed of the fluorescent substance and the piezoelectric material, various methods can be used for producing the composite material, but the following method is preferably used.

That is, a 60th aspect of the present invention is a method for producing a composite material which mainly comprises a fluorescent substance and a piezoelectric material and emits light depending on the time rate of change of stress.
A step of melting a mixture containing at least Sr, Al, and Eu and a glass-forming substance, quenching once from this molten state to generate a glass phase, and a powder and a piezoelectric material obtained by crushing the glass phase are provided. SrAl ₂ O ₄ : Eu is mixed from the glass phase by mixing and heat treatment.
It is characterized by having a step of depositing fine particles.

The sixty-first invention of the present invention is a method for producing a composite material, which is mainly composed of a fluorescent substance and a piezoelectric material, and whose emission intensity changes depending on the time rate of change of stress,
A step of melting a mixture containing at least Sr, Al, and Eu and a glass-forming substance, quenching once from this molten state to generate a glass phase, and a powder and a piezoelectric material obtained by crushing the glass phase are provided. SrAl ₂ O ₄ : Eu is mixed from the glass phase by mixing and heat treatment.
It is characterized by having a step of depositing fine particles.

Using a substrate having an actuator function,
A two-dimensional array of light emitting elements can be easily realized by printing the ink containing the fluorescent substance according to the present invention in a dot shape using a printer or the like. That is, a sixty-second invention of the present invention provides a substrate having an actuator function, and a dot-shaped substance provided on the substrate in a predetermined arrangement and containing a fluorescent substance that emits light depending on a time change rate of stress. A light-emitting element characterized by having.

The 63rd invention of the present invention is a dot including a substrate having an actuator function and a fluorescent substance provided on a substrate in a predetermined arrangement and having a luminescent intensity varying depending on a time change rate of stress. A light-emitting element including a substance.

A sixty-fourth aspect of the present invention is a substrate having an actuator function, and a dot-shaped substance provided on the substrate in a predetermined arrangement and containing a fluorescent substance which emits light depending on a time change rate of stress. A method of manufacturing a light emitting device having the above-mentioned, wherein the dot-shaped substance is formed by printing on a substrate using an ink containing a fluorescent substance.

A sixty-fifth aspect of the present invention is a dot having a substrate having an actuator function and a fluorescent substance provided on the substrate in a predetermined arrangement and having a luminescent intensity that changes depending on a time change rate of stress. A method for manufacturing a light-emitting element having a dot-like substance, wherein the dot-like substance is formed by printing on a substrate using an ink containing a fluorescent substance.

The above printing is typically performed by a printer. The dot-shaped substance is provided on the substrate in a desired arrangement, but is typically provided periodically. In this case, elements having an actuator function are periodically embedded in the surface of the substrate. A substrate having a polymer actuator function may be used as the substrate. This polymer actuator is, for example, a water-soluble non-electrolyte polymer gel having a thermal displacement function, an electrolyte polymer gel that is displaced by pH, a combination of a polymer compound that is electrically displaced and a surfactant, and a polyvinyl alcohol type. At least one material selected from the group consisting of materials and polypyrrole materials is used.

With the fluorescent substance or the composite material according to the present invention, a flexible light emitting material can be obtained.
It can be used, for example, as a wearable material. That is, a sixty-sixth aspect of the present invention is a film-shaped, liquid-droplet-shaped, rod-shaped, or rod-shaped material in the two-dimensional plane of the substrate, which comprises a material containing at least a fluorescent substance that emits light depending on the rate of change of stress with time. The flexible light emitting material is characterized in that a plurality of materials provided in the shape of stripes or bulk ceramics are connected by a flexible connecting means.

The sixty-seventh aspect of the present invention is to form a film, a droplet, or a dot in a two-dimensional plane of a substrate by using a material containing at least a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time. It is a flexible light-emitting material characterized in that a plurality of materials provided in the shape of a ring, a rod, a stripe or a bulk ceramic are connected by a flexible connecting means. These flexible luminescent materials are made macroscopically flexible by connecting the above-mentioned substrates with fibers or cords in a manner similar to that used in the production of traditional Japanese armor. It can be said to be a thing.

The fluorescent substance or composite material according to the present invention can easily emit light by applying ultrasonic waves as described above. Such an ultrasonic luminescent substance can be obtained by various methods, but preferably, it can be obtained by the following method. Further, this ultrasonic luminescent substance can be used, for example, for a traffic sign using luminescence. That is, the sixth aspect of the present invention
The invention of 8 is characterized by being obtained by subjecting a crystalline material, in which only one kind of rare earth element is doped in a matrix of an oxide of an alkaline earth metal and aluminum, to a reduction treatment at a temperature of 500 ° C. or higher. It is an ultrasonic emitting substance.

The 69th invention of the present invention is to subject a crystalline material, in which only one kind of rare earth element is doped in a matrix of an oxide of an alkaline earth metal and aluminum, to a reduction treatment at a temperature of 500 ° C. or higher. It is a traffic sign that is characterized by using a material containing at least an ultrasonic luminescent substance obtained by the above, and emitting light by applying an ultrasonic wave.

The fluorescent substance according to the present invention can be used in various electronic devices having a light emitting display unit, a light emitting system, a display system, etc., and is used as a composite material in combination with other substances as required. May be. That is, the 70th invention of the present invention is an electronic device having a light-emitting display unit, wherein the light-emitting display unit uses a fluorescent substance that emits light depending on a time change rate of stress. .

The seventy-first invention of the present invention is characterized in that, in an electronic device having a light emitting display portion, a fluorescent substance whose light emission intensity changes depending on a time change rate of stress is used for the light emitting display portion. It is an electronic device.

The 72nd aspect of the present invention is a display section using a fluorescent substance which emits light depending on the rate of change of stress with time.
A light emitting system comprising: an ultrasonic wave source for irradiating an ultrasonic wave to a display unit.

A seventy-third aspect of the present invention is a display section using a fluorescent substance whose emission intensity changes depending on the rate of change of stress over time, and an ultrasonic source for irradiating the display section with ultrasonic waves. Is a light emitting system.

The seventy-fourth aspect of the present invention is a display section using a fluorescent substance which emits light depending on the rate of change of stress with time.
It is a display system characterized by having an ultrasonic source for irradiating an ultrasonic wave to a display section.

A seventy-fifth aspect of the present invention is a display section using a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time, and an ultrasonic source for irradiating the display section with ultrasonic waves. It is a display system characterized by having.

The seventy-sixth aspect of the present invention is characterized in that a fluorescent substance that emits light depending on the rate of change of stress with time is used, and light emission is controlled by the rate of change of stress with time of the fluorescent substance. It is a light emitting method.

The seventy-seventh aspect of the present invention uses a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time,
It is a light-emitting method characterized in that the light-emission intensity is controlled by the time change rate of the stress of the fluorescent substance.

According to the present invention configured as described above, it is possible for a human to lightly touch a fluorescent material or a composite material with his or her hand or finger to bend them greatly with a soft feeling, resulting in stress emission. In addition, it becomes possible to illuminate a predetermined portion by using an electric signal from the outside and utilizing piezoelectric vibration or the like.

One important application of the composite material according to the present invention is the skin or external coating of products such as entertainment robots that are actually touched by human users. In that sense, the feature that glows when touched is remarkably attractive, and is considered to irritate consumers.

On the other hand, although it is a physical effect, since functional touch is regarded as an input signal in the first place, an energy-saving material or product can be obtained. Further, even when a predetermined portion is illuminated by an external electric signal, it is not necessary to inject current unlike electroluminescence or a light emitting diode, so that power consumption can be reduced.

The present invention is a material innovation for the new entertainment industry. In other words, many conventional products reflected the logic of the creator only, but it may become more interesting by the user's ideas or dialogue, such as how to handle the fluorescent substance or composite material according to the present invention. Therefore, the interest of users will be high and it will have a great impact on the industry. In particular, when the material according to the present invention is used as the skin of an entertainment robot, it emits light when the user deforms or when the robot itself performs stress work on the skin such as bending a joint. . The idea of this material has the potential to revolutionize not only the entertainment industry but also the optical field as a whole.

[0125]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings. First, a method for producing SrAl ₂ O ₄ : Eu ceramics by a normal solid-phase reaction method will be described. As a manufacturing procedure, first, a predetermined amount of the following substances as raw materials are mixed in a ball mill for about 20 hours.

SrCO ₃ 0.39 mol = 147.6292 × 0.39 = 57.557388 g Al ₂ O ₃ 0.4 mol = 101.96128 × 0.4 = 40.784512 g Eu ₂ O ₃ 0.002 mol = 351.9182 X 0.002 = 0.7038396 g B ₂ O ₃ 0.032 mol = 69.6182 x 0.032 = 2.2277824 g

Thereafter, calcination in air at 1400 ° C., 14
Calcination in oxygen at 00 ° C, H ₂ (5%) N at 1300 ° C
_{2 The} synthesis was performed by a process called reduction heat treatment in an atmosphere.
The X-ray diffraction patterns at each stage at that time are shown in FIGS. At the stage of calcination in air at 1400 ° C (Fig. 2), almost the target crystal phase was formed, and the resulting substance is a known paper [F. Hanic, TY Chemekova and J. Majling,
J. Appl. Phys., 12 (1979) 243], all of them were indexed in the monoclinic system and found to be a single phase.

Next, polyester resin (made by Buehler
(Castolite Resin) and the above SrAl ₂ O ₄ : Eu powder at a weight ratio of 1: 2 to form a sheet having a size of several cm square, which is left to stand for a whole day and night. Was produced. Here, the diameter of the powder fine particles of SrAl ₂ O ₄ : Eu is 100 nm or less. It should be noted that there is no report on the use of polyester in the above-mentioned report of Nemoto Special Chemical Co., Ltd. On the other hand, Kyushu Institute of Technology mainly uses epoxy resin, which is a material system not reported here either. The sheet produced here was a thin sheet (underlay) having a thickness of less than 1 mm, and it was confirmed that it strongly shines only by bending it gently in the dark. The situation at that time is shown in FIG.

FIG. 5A shows a sheet in a bright place before folding, FIG. 5B shows a darkened place (where bending starts), and FIG. 5C shows a case where the place where it is folded and the place where it is held shines. In 5D, the case where the entire sheet shines when folded is shown. Only the inventor of the present invention has succeeded in making the light easily by human power.

In the experimental report by Xu and Akiyama et al. Of the Kyushu Institute of Industrial Technology, many tons of pressure are applied to the bulk body of the epoxy resin mixture, and light is emitted even when touched lightly by a human. No report has been made to the inventor's knowledge. Thus, the fact that a material that shines by a simple bending operation was obtained is extremely useful as an artificial skin material for entertainment robots and the like. FIG. 6 shows a simple image diagram thereof. In FIG. 6, the above-mentioned sheet is provided as artificial skin on the body of a dog-type entertainment robot, and light emission is generated by touching the artificial skin with a fingertip of a human hand. It is considered that the inorganic-organic / composite sheet that emits light only by lightly touching it has not only the above-mentioned research on the functional artificial skin material but also a considerable ripple effect to other fields.

Next, SrAl ₂ O as a stress-stimulated luminescent material is used.
₄ : The mixing ratio of the Eu powder and the resin material (expressed by weight%) will be described. By the same method as above, SrAl ₂ O
₄ : Mixing Eu powder and polyester at a weight ratio of 10%
Was changed to 80%, and a sheet-shaped molding was tried. The shape of the sheet is 10 mm × 25 mm and the thickness is about 0.25 mm. Speaking only in this experiment, when 70% or less, good sheet moldings were formed in all cases, but when 80%, it was likely to be broken, resulting in poor mechanical reliability. FIG. 7 shows SrAl ₂ O ₄ : E in this sheet.
The correlation between the weight ratio (weight content) of u powder and the emission intensity is shown. Considering only the emission characteristics, SrAl ₂ O ₄ :
The higher the Eu filling rate, the higher the emission intensity obtained, but it is difficult to commercialize it due to poor mechanical reliability. From this result, it is considered that about 30 to 75% is preferable. However, in essence, it is considered that a good sheet-shaped molded body can be formed even if the content is 80% or more.

Although the composite material used here is stress-stimulated luminescence, it is actually difficult to catch the luminescence clearly with the eyes under bright conditions in the daytime.
It is a problem of emission intensity, and it can be clearly understood by using photoexcitation such as ultraviolet rays, but in the case of stress emission, it is not always clear whether the excitation intensity is still low or the efficiency is low, but anyway it is obvious that it emits light during the daytime I don't know the condition. Therefore, it can be considered to be used at night as an effective use time zone. However, it can be used without problems in a dark room.

Here, a very important resin mixture sheet of SrAl ₂ O ₄ : Eu + Dy powder developed by Nemoto Special Chemical Co., Ltd., in which two kinds of rare earth elements are doped,
The comparison result of the afterglow characteristics in the dark of the mixed sheet of SrAl ₂ O ₄ : Eu and the resin developed by the present inventors will be described. The mixing ratio is the same for both, and powder: resin = 1: 2. The result is shown in FIG.

8A to 8E, SrAl ₂ O ₄ : E is shown on the left side.
The behavior of SrAl ₂ O ₄ : Eu + Dy is shown on the right side of u.
The appearance and color tone in a bright place are exactly the same. However, the light emission state after turning off the lighting in the room is very different, and the sensitivity to the eyes becomes considerably darker in less than 1 minute, whereas the latter was originally developed as a long afterglow. Yes, it can be seen that it continues to shine considerably.

Conversely, this means that the latter material system is not suitable as artificial skin for the purpose of stress luminescence. That is, even in a dark place, light is emitted before the stress is applied, and a large ratio of the emission intensity before and after the stress is generated cannot be obtained. Therefore, it is proved that SrAl ₂ O ₄ : Eu, which does not exhibit long afterglow characteristics, is suitable for such an application.

Next, SrAl produced by the present inventor
_The results of evaluating the light emission characteristics of the ₂ O ₄ : Eu powder and the SrAl ₂ O ₄ : Eu + Dy powder developed by Nemoto Special Chemical Co., Ltd. for comparison will be described. FIG. 9 shows an ultraviolet excitation-emission spectrum (FIG. 9A) of the SrAl ₂ O ₄ : Eu powder produced by the present inventors and its afterglow characteristic (FIG. 9B).
FIG. 10 shows SrAl ₂ O ₄ : Eu + Dy powder [trade name Luminova (G-300C) manufactured by Nemoto Special Chemical Co., Ltd.]
The ultraviolet excitation-emission spectrum (FIG. 10A) and the afterglow characteristic thereof (FIG. 10B) are shown respectively.

In the preparation of SrAl ₂ O ₄ : Eu powder, it was confirmed in advance that one treatment before reduction was sufficient, and then calcination was performed in an oxygen atmosphere at 1400 ° C. for 2 hours, and then calcination was performed. , reduction treatment (N ₂ in 4% H _2), 1300
A sample for measurement was prepared by conducting the test at 2 ° C. for 2 hours. It has been confirmed that this sample is a single phase. The temperature of the reduction treatment may be at least 500 ° C. or higher.
It goes without saying that the temperature is not limited to ° C.

In both cases, the main peak of the light emission has a wavelength near 520 nm and exhibits a green color. However, looking at the afterglow (decay) characteristics after the ultraviolet irradiation is stopped, as described above, the S
It can be confirmed that the emission intensity of rAl ₂ O ₄ : Eu declines much faster. Note that FIG. 9A and FIG.
The emission spectrum of A is an overlay of the results measured every 25 milliseconds, and it can be seen that the intensity of the emission spectrum is decreasing every moment.

Now, regarding the emission spectra and the mechanism thereof, a band image relating to the emission of SrAl ₂ O ₄ : Eu is shown in FIG. In FIG. B. Is the valence band, C.I. B. Indicates the conduction band. The light emission mechanism has been found to some extent based on the past research results of Matsumoto et al. Of Nemoto Specialty Chemicals Co., Ltd. and Xu et al. Of Kyushu Institute of Industrial Technology, and the evaluation of Nakazawa Kogakuin University and Denei et al. Of Niigata University. ing. Basically, since the wavelength of stress emission is the same as the wavelength of photoluminescence upon excitation with ultraviolet light, it is only necessary to consider the understanding of photoluminescence as the basis. However, energy change due to stress is another point to be considered. As shown in FIG. 11, in the energy transition process, first, so-called charge transfer transition is performed in which Eu ²⁺ takes electrons in the valence band to become monovalent Eu ⁺ . Then, holes are generated in the valence band. The holes in this valence band are bound to Eu ⁺ , which is effectively charged with a negative charge, in the excited state, and Eu is a new excited state.
It is believed that ²⁺ are formed. Then, light is emitted in the form of recombination with holes, and about 2. due to d → f transition.
It is considered that light emission of 4 eV (520 nm) occurs.

Next, as a characteristic of the composite material of SrAl ₂ O ₄ : Eu and resin, the light emission phenomenon in both the process of applying and releasing the pressure is shown in FIG. Figure 12A
˜E show the results of observing the light emission characteristics by applying and releasing the pressure, and reproduce the time-lapse shooting from the video shooting. FIG. 12A shows the sample placed on the press table.
There is some afterglow in the dark state before pressurization (Fig. 12).
B). Light is emitted strongly at the moment of pressurization (FIG. 12C), and disappears when the pressure is maintained (FIG. 12D). Figure 1
2E shows a state in which the pressure is released. As can be seen from the above, the stress-stimulated luminescence referred to here means the luminescence caused by the time derivative of the stress, if it is physically accurately expressed. This is also confirmed by the fact that the light emission becomes stronger as the pressurization speed is actually increased.

As described above, it was found that the emission intensity greatly depends on the time derivative of stress or the pressurizing rate, and therefore the present inventor conducted an experiment in the expectation of emission under ultrasonic vibration. This experiment is considered to be the first in the world. The ultrasonic transducer used in the experiment was made by Honda Electronics Co., Ltd., and was equipped with a horn in the oscillating unit. The specifications were that the resonance frequency was 39.30 kHz, the resonance impedance was 180Ω, and the capacitance was 2480 pF. . SrAl ₂ O ₄ : E was added to the ultrasonic horn in this resonance state.
When a sheet in which u and a polyester resin were composited was brought into contact with each other, light emission was confirmed as expected. The result is shown in FIG.

FIG. 13A shows the appearance of the ultrasonic horn, and FIG.
FIG. 13B shows the light emission state in the dark field, and FIG. 13C shows the light emission state reproduced by using the video night shot photographing function. From FIG. 13B and FIG. 13C,
It is clear that it emits light upon receiving ultrasonic waves. This is because the wave of vibration propagates in the composite sheet and SrAl
It is considered that ₂ O ₄ : Eu fine particles have reached and emitted light. However, the light is still weak unless it is brought into strong contact with the ultrasonic horn stage, and it is considered that light can be emitted more efficiently if only the propagation loss of ultrasonic waves can be suppressed. In addition, in order to confirm the effect of heat generation on the contact surface, we conducted an experiment to separately contact a heat-generating part such as a hot plate and check for the presence or absence of light emission, but from these experiments no visible light emission was observed. Since it was not done, it was clearly proved to be ultrasonic emission. This is expected from the thermoluminescence study by Denai et al. Of Niigata University mentioned above, and this SrAl ₂ O ₄ : Eu powder has a large thermoluminescence emission peak (related to the trap) at 230K. However, it has been reported that the strength decreases to a fraction of a room temperature or higher.
That is, it can be seen that even if exposed to a temperature higher than room temperature, it is difficult to emit light only by heat. For the purpose of increasing the efficiency of this ultrasonic emission, an experiment was conducted using an oscillator with a higher frequency of MHz. The vibrator used here is of the same type as that used in ultrasonic humidifiers and the like, and is in the form of a disk having a diameter of about 2 cm and a thickness of 1 mm. Stick a sheet on the surface and frequency 2.4M
FIG. 14 shows a state where vibration is applied at Hz. 14
A is the state where the vibrator is off, and FIG. 14B is the state where the vibrator is on.

The mode of piezoelectric vibration is mainly longitudinal vibration in the thickness direction. A clear, more intense luminescence was observed (Fig. 14B). It is considered that this is because the high frequency vibration has a larger acceleration. From the results of such basic experiments,
It is considered that this material can emit light using surface waves or the like. Further, it is considered that ultrasonic waves can be applied to the air to illuminate a board at a distance. In this way, the significance of directly converting the vibration energy into light energy is very significant.

When the technical positioning is repeated again, the SrAl ₂ O ₄ : Eu is also observed to have thermoluminescence emission, but the research report by referring to stress emission is Kyushu Industrial Technology Research. Most of the groups are Xu and Akiyama. They reported that not only ceramic solids, but also composites with resins (but only epoxy-based resins) emit light when hit or pressed, but both target bulky, bulky objects. is there. None of the world's reports on experiments that give ultrasonic vibrations directly to a substance, as well as emitting light by simply touching it, have not been made worldwide.

As described above, the fluorescent SrAl ₂ O ₄ : E
In a composite sheet of u powder and polyester resin,
For the first time, the phenomenon of emitting light when contacted with an ultrasonically vibrating object was observed. This shows the possibility that the light emission of a solid can be controlled by ultrasonically controllable ultrasonic vibration rather than by very simple mechanical energy. On the other hand, it was also confirmed that the same sheet easily emits light by a simple bending (bending) operation. From the aspect of application to artificial skin, it is significant that it was confirmed to be effective in two aspects, electrical control and spontaneity.

Based on these results, the following element is proposed. That is, the composite material according to the present invention formed into a sheet can be used as artificial skin of a robot used for so-called entertainment or various other purposes. The conceptual diagram in this case is shown in FIG.
Shown in. As can be seen from FIG. 15, when the user touches any place on the skin, not only the place spontaneously emits light, but also two pieces of information about the position touched by another element and the strength. Can be stored in the CPU once, and after a proper time shift, the skin at a predetermined position can be illuminated. An image diagram in this case is shown in FIG. FIG.
This shows that the dog's cheeks, which had been patted on the head with human hands, appear to be red hot, after a short while. This is easily possible with this composite material and the system of FIG.

Next, the components of the artificial skin will be described. Artificial skin requires some flexibility.
Therefore, as described above, it is natural to use an elastomer such as a resin as the matrix, and it is also possible to sandwich it with a rubber or the like to make it shine. Furthermore, not only such a method but also SrAl ₂ O
₄ : It is also possible to realize light emission by making the Eu ceramics itself into a fiber shape, a sponge shape, or a network shape so as to have some flexibility by itself. An image diagram in that case is shown in FIG.

FIG. 17 shows an image of the structure of artificially colored skin, and shows how light is emitted by the compression of the network structure by the application of an external force.
FIG. 17 shows a ceramic framework structure in addition to the sponge structure. To form such a structure, a method of washing away the particle portion with acid or the like after sintering the ceramic and leaving only the grain boundary portion Is commonly used.
When SrAl ₂ O ₄ : Eu is left at the grain boundary, SrAl
₂ O ₄ : Eu may be mixed with a substance that does not easily react with Eu, and after firing, the substance may be washed with an acid or the like. A specific example is ZnO-N.
The case of b ₂ O ₅ system is described in the following paper.・ Kenya Hamano, Akio Sayano, Zenbei Nakagawa, Journal of Ceramic Industry Association, 91
(1983) 309-317

Next, as a method of obtaining a similar flexible structure, there is an inorganic / organic hybrid composite material. Among inorganic-organic nanocomposites, SrAl ₂ O ₄ : Eu
Ideally, only the sites are selectively present as nanocrystals. In this case, the matrix portion is an inorganic / organic hybrid composite material. This image is shown in FIG. FIG. 19 shows a state in which a sheet piece of this flexible inorganic / organic hybrid composite material is bent by being sandwiched between the fingertips of a person.

The wavy line portion in FIG. 18 is -Si-O-Si.
It is a siloxane bond of −, and has a M—O site (here, Sr and Al are considered as M, and Sr—O and Al—O are considered) at the terminal part thereof. In this inorganic-organic hybrid composite material, mechanical displacement propagates to the siloxane bond, which is spatially interspersed with Sr.
Light emission occurs when reaching the -O and Al-O sites.

To prepare this inorganic / organic hybrid composite material, tetraethoxysilane (Si (OC
₂ H _{5) 4,} siloxanes is hydrolyzed product of TEOS) a (-Si-O-Si-) may be used as a raw material, conveniently, polydimethylsiloxane (HO- (Si
_{(CH 3) 2) -OH,} PDMS) can be used as a raw material. Further, in order to form a light emitting site, an aluminum alkoxide (for example, Al (—O—CH (C
H _{3) 2) 3)} or strontium alkoxide (e.g., Sr (-O-CH (CH 3) 2) 3) a may be reacted together. Under appropriate reaction conditions, dehydration / condensation reaction occurs to obtain a desired hybrid structure. The specific manufacturing method is described in detail in the following paper.・ Noriko Yamada, Ikuko Yoshinaga, Shingo Katayama, Material Integration 12 (1999) 51-56

Further, as another idea, as a matrix surrounding the stress-stimulated luminescent material, an organic conductive material such as polypyrrole capable of taking in ions is used, and it is bent at the same time by facing it with an external electrode. It is also possible. Next, the case where this stress-stimulated luminescent material is used as a material for illuminating a two-dimensional surface will be described.
In this case, current injection is not required unlike a semiconductor laser or a light emitting diode, so that energy can be saved accordingly.

First, a light emitting element in which a stress light emitting material is laminated on a piezoelectric thin film such as PZT laminated on Si can be considered. FIG. 20 shows a method of manufacturing two types of light emitting devices that are composited with this piezoelectric material. As shown in FIG. 20, for example (0
For example, a CeO ₂ film having a (001) plane orientation is epitaxially grown as a buffer layer 12 on a Si substrate 11 having a (01) plane orientation (FIGS. 20A and 20B), and a lower electrode layer 13 having a (001) plane orientation is formed thereon. SrRuO ₃
A perovskite-type conductive thin film such as a thin film is epitaxially grown (FIG. 20C), and a perovskite-type thin film such as PZT having a (001) plane orientation is epitaxially grown thereon (FIG. 20D).

The subsequent process depends on the type of the light emitting device. In one type of light emitting device, as the upper electrode layer 15 on the piezoelectric thin film 14, for example, SrRuO having a (001) plane orientation is used.
₃ A perovskite type conductive thin film such as a thin film is epitaxially grown (FIG. 20E), and the stress light emitting layer 1 is further formed thereon.
As S6, for example, SrAl ₂ O ₄ : Eu or a composite material of SrAl ₂ O ₄ : Eu or this is laminated (FIG. 20F), and finally, as the transparent cap layer 17, a thin film such as glass or transparent organic resin is formed (FIG. 20G). . Accordingly, the piezoelectric longitudinal vibration generated in the piezoelectric thin film 14 due to the voltage applied between the lower electrode layer 13 and the upper electrode layer 15 is properly propagated to the stress light emitting layer 16, and the light emitting element in which efficient light emission occurs can get.

In another type of light emitting device, the piezoelectric thin film 1
The stress-stimulated luminescent layer 16 is directly laminated on the layer 4 (FIG. 20H), and finally a transparent conductive film such as ITO or CuAlO ₂ is laminated and covered as the upper transparent electrode layer 18 (FIG. 20I). Here, when a thin film of SrAl ₂ O ₄ : Eu is laminated as the stress-stimulated luminescent layer 16, this thin film is preferably laminated with the piezoelectric thin film 14 in an epitaxial lattice match. From the above,
Piezoelectric longitudinal vibration generated in the piezoelectric thin film 14 due to the voltage applied between the lower electrode layer 13 and the upper transparent electrode layer 18 is properly propagated to the stress light emitting layer 16, and a light emitting device in which efficient light emission is obtained can be obtained. .

The above-mentioned two types of light emitting elements are so-called
Electron vibration is used, but a similar method
Sex waves can also be used. Utilizing this surface acoustic wave
FIG. 21 shows a method of manufacturing a light emitting device. As shown in Figure 21
First, for example, a Si substrate 21 having a (001) orientation is formed on a Si substrate 21.
As the buffer layer 22, for example, CeO having a (001) plane orientation ₂
The film is grown epitaxially (FIGS. 21A and 21).
B), and a piezoelectric thin film 23 formed thereon, for example, the (001) plane
Epitaxy of perovskite type thin films such as PZT
Growth (FIG. 21C). Furthermore, on this piezoelectric thin film 23
, For example, SrRuO with (001) orientation₃Thin film
Epitaxially grown rovskite type conductive thin film
And pattern them to face each other
Two comb-shaped electrodes 24 and 25 are formed (FIG. 21D). Most
Later, as an example of the stress emission layer 26 between the comb-shaped electrodes 24 and 25
For example SrAl₂O_Four: Eu or compound of this with resin, etc.
The composite material is laminated (FIG. 21E). This allows the comb-shaped electric
It is generated in the piezoelectric thin film 23 by the voltage applied to the pole 24
The surface acoustic wave propagates well to the stress-stimulated luminescent layer 26, resulting in good efficiency.
A light emitting device that emits a large amount of light can be obtained.

Next, an example in which the above light emitting element is integrated with a MOSFET will be described. FIG. 22 shows an example of a light emitting element in which the above-described surface acoustic wave type light emitting element is integrated with a MOSFET. As shown in FIG. 22, for example, a p-well 32 is formed on an n-type Si substrate 31, and a CeO ₂ film having a (001) plane orientation is formed on the surface of the p-well 32 as a field insulating film 33 for element isolation. Has been done. A gate insulating film 34 such as a SiO ₂ film is formed on the surface of the active region surrounded by the field insulating film 33.
A gate electrode 35 made of, for example, polycrystalline Si doped with impurities or polycide is formed thereon. p
An n ⁺ type source region 36 and a drain region 37 are formed in the well 32 in a self-aligned manner with respect to the gate electrode 35. The gate electrode 35, the source region 36, and the drain region 37 allow the n-channel M
The OSFET is configured.

On the other hand, a perovskite type thin film such as PZT having a (001) plane orientation is laminated as a piezoelectric thin film 38 on the field insulating film 33, and (00) is formed thereon.
1) Two comb electrodes 39, 40 made of a perovskite type conductive thin film such as a plane-oriented SrRuO ₃ thin film are formed so as to face each other. These comb-shaped electrodes 39, 40
In the meantime, as the stress emission layer 41, for example, SrAl ₂ O ₄ : Eu
Alternatively, a composite material of this and resin or the like is laminated.
The piezoelectric thin film 38, the comb-shaped electrodes 39 and 40, and the stress light emitting layer 41 constitute a surface acoustic wave light emitting cell.

An interlayer insulating film 42 such as a SiO ₂ film is formed so as to cover the MOSFET and the light emitting cell. Connection holes 43 are formed in the gate insulating film 34 and the interlayer insulating film 42 in the portion above the drain region 37,
A plug 44 made of, for example, polycrystalline Si or W doped with impurities is buried in the connection hole 43. Further, connection holes 45 and 46 are formed in the interlayer insulating film 42 above the comb electrodes 39 and 40. The plug 44 and the comb-shaped electrode 39 are connected by the metal wiring 47 through the connection hole 45. Further, the metal wiring 48 is connected to the comb-shaped electrode 40 through the connection hole 46.

In the MOSFET integrated light emitting device having the above-mentioned structure, the drain region 3 of the MOSFET is formed.
Since 7 and the one comb-shaped electrode 39 provided on the piezoelectric thin film 38 that oscillates the surface acoustic wave are electrically connected, the light emission from the light emitting cell can be controlled by switching the MOSFET. In other words, this MO
The SFET integrated light emitting device can be driven by an active matrix. Therefore, by using an active matrix circuit as shown in FIG.
It is possible to form an ET-integrated two-dimensional light emitting device. FIG. 23
The light emitting cell is shown by □. The source line is connected to the source region 36 of the MOSFET in each pixel section. The gate line is the gate electrode 3 of the MOSFET in each pixel section.
It is connected to 5.

Next, a light emitting device using mixed ceramics will be described. An example thereof is shown in FIG. As shown in FIG. 24, in this light emitting device, mixed ceramics in which a stress-stimulated luminescent material and a piezoelectric material are combined are used, and piezoelectric ceramics microcrystals such as PZT microcrystals 51 are used as particles, and grain boundaries (matrix part) are used. ), For example, SrAl ₂ O ₄ : Eu52 is formed as a stress-stimulated luminescent material. Therefore, as shown in FIG. 25A, the electrodes 54, so as to sandwich the ceramic material 53 having such a microstructure,
55 is provided, and an AC electric field is externally applied between these electrodes 54 and 55 to cause piezoelectric vibration, as shown in FIG. 25B. As a result, the grain boundary portion can be made to shine.

The method for producing this mixed ceramic material is as follows:
It is as follows. That is, for example, the above-mentioned Sr
Similar to the method for producing Al ₂ O ₄ : Eu, first, for example, SrCO ₃ , Al ₂ O ₃ , Eu ₂ O ₃ and B _{2 are used} as raw materials.
After mixing a predetermined amount of O ₃ in a ball mill, the mixture is heat-treated and melted, and the molten state is once rapidly cooled to form a glass phase. Next, this glass phase is crushed into powder, and this is mixed with PZT microcrystallized,
By heat treatment, SrAl ₂ O ₄ : Eu is precipitated from the glass phase at the grain boundary portion of PZT microcrystal.

Next, an example of a method of manufacturing a light emitting element using an actuator substrate will be described. In this example, as shown in FIG. 26, a stress-stimulated luminescent ink (which can also be called a kind of paint) containing, for example, SrAl ₂ O ₄ : Eu fine particles as a stress-stimulated luminescent material is ejected in dots on an actuator substrate 61 by an inkjet method. Stress emission dot 62
Are periodically formed in the X and Y directions.

The actuator substrate 61 is composed of a polymer gel element, a piezoelectric element, an ultrasonic element, a giant magnetostrictive element, a shape memory alloy element, a hydrogen storage element, a heating element (bimetal, etc.) and the like. Among them, in the polymer gel element,
Heat-displaceable water-soluble non-electrolyte polymer gels, especially those having an ether group in the side chain, such as polyvinyl methyl ether (PVME) and poly-N-isopropylacrylamide (P
NIPAM) is one of the candidate materials. In addition, polyacrylonitrile (PA), an electrolyte polymer gel that changes with pH
N), a combination of polyacrylamide-2-methylpropanesulfonic acid (PAMPS) capable of electric displacement and a surfactant, and a polyvinyl alcohol-based material are also strong candidate materials. Furthermore, polypyrrole and the like are also candidate materials for organic molecular actuators.

Whether the surface acoustic wave is used or the piezoelectric longitudinal vibration is used as the drive mode of the actuator substrate 61,
Alternatively, mechanically generated surface wrinkles may be used. There is a method of periodically inserting the above-mentioned actuator material into this actuator substrate 61 in order to bring about a temporal change in the surface. FIG. 26 shows an example in which the actuator material 63 is inserted into the actuator substrate 61 periodically in the X direction with the insertion direction being the Y direction. In this example, the periodically inserted actuator material 63 provides the periodicity of displacement of the surface of the actuator substrate 61.

Next, a road sign light emitting system using ultrasonic waves will be described. FIG. 27 shows an example thereof. Figure 27A
As shown in,
A necessary mark is formed using the stress-stimulated luminescent material or the composite material according to the present invention on the surface of the sign portion, and the ultrasonic oscillator is attached to the automobile. Then, as shown in FIG. 27B, when the ultrasonic wave generated by the ultrasonic oscillator hits the marker portion, stress emission occurs, and the mark is raised so that the driver can recognize it.

Next, the artificial skin on which a kind of optical nerve network is formed will be described. An example thereof is shown in FIG. FIG. 28
In this example, in this example, a plastic fiber (optical fiber) is provided in a two-dimensional array penetrating the skin layer made of artificial skin material, and a spherical stress emission composite is provided at one end of each plastic fiber on the surface side of the skin layer. Material is attached. This stress-luminescent composite material is, for example,
It consists of SrAl ₂ O ₄ : Eu and a polyester resin.
In this artificial skin, for example, when a human finger touches the surface, light emission occurs from the stress-stimulated luminescent composite material at that site,
The light passes through the plastic fiber and is emitted in pulses from the other end to the back side of the skin layer. That is, the contact of the finger with the surface of the skin layer and its contact site, in other words, contact information, can be detected from the light emission from the back surface side of the skin layer and its emission position. It can be said that the optical nerve network is formed in the artificial skin.

FIG. 29 shows an experimenter using an optical fiber in which a composite sheet of SrAl ₂ O ₄ : Eu and a polyester resin, which emits light depending on the time change of stress, is brought into contact with one end face thereof. Shows how one hand is supporting and the other hand is trying to apply an external force to this seat. Here, a single rod fiber having a diameter of 8 mm and a cladding layer thickness of 125 μm is used as the optical fiber.

FIG. 30 shows a state in which the environment is darkened in the arrangement shown in FIG. 29, and shows a state before an external force is applied to the composite sheet. As can be seen from FIG. 30, in this state, no external force is applied to the composite sheet, so that light emission does not occur and the entire structure is black.

FIG. 31 shows a state at the moment when an external force is applied to the composite sheet with the environment kept dark in the arrangement shown in FIG. From FIG. 31, in addition to light emission from the composite sheet to which external force is applied, light emission from the other end face of the optical fiber can be seen. The light emission from the other end face of this optical fiber means that the light emitted from the composite sheet was transmitted through the optical fiber and emitted from the other end face of this optical fiber. As a result, in principle, the optical transmission of the light emitted from the above composite sheet by the optical fiber was experimentally confirmed, which means that the feasibility of the artificial skin having the above optical nerve network was proved. To do.

FIG. 32 shows a wavelength λ = 520 nm emitted from the other end surface of the optical fiber for a total of 2 seconds before and after the composite sheet is brought into contact with one end surface of the optical fiber and external force is applied to the composite sheet. 20 ms for the intensity of light (wavelength of stress emission) (luminescence intensity)
The results of monitoring at ec intervals are shown. From FIG. 32, it is clear that light having a wavelength of 520 nm is emitted from the other end face of the optical fiber by applying an external force to the composite sheet. This reconfirms the optical transmission of the light emitted from the composite sheet through the optical fiber.

FIG. 33 shows three artificial light-emitting hairs in which a plastic tube, for example, a vinyl tube, is filled with a composite material in which SrAl ₂ O ₄ : Eu and a polyester resin are composited. The diameter of these artificially luminescent hairs is about 1 mm. These artificial light-emitting hairs can be manufactured as follows, for example. That is, SrA
l ₂ O ₄ : While the fine particles of Eu and the polyester resin are in a liquid state before solidifying, a tube made of, for example, vinyl is attached to the tip of the injection needle of the syringe, and this tube is put into the composite material in the liquid state. Fill the tube with the composite material by sucking up the composite material by operating a syringe. Then, the tube is removed from the injection needle, and the composite material in the tube is solidified. In this way, artificial luminous hair is manufactured. It should be noted that it is conceivable to fill the composite material into the cylinder of the syringe and put it into the tube by pushing it out from the injection needle, but in this method, in general, bubbles easily enter and pressurization is not easy. There is inconvenience.

FIG. 34 shows the appearance of thin artificial luminescent hair having a diameter of about 0.6 mm produced by the above method. Fig. 35
Shows the appearance on the verge of bending the artificial light emitting hair having a diameter of 1 mm produced by the above method. FIG. 36 shows the appearance when the artificial light-emitting hair with a diameter of 1 mm produced by the above method was bent in a darkened environment. From FIG. 36, the state of light emission was clearly seen, and light emission from the artificial light-emitting hair-like tube was confirmed. This proved that it can be applied to entertainment robots and other products as artificial luminescent hair.

37A to 37E show light emission from the sample when the SrAl ₂ O ₄ : Eu single crystal thin piece was placed on the 2.4 MHz ultrasonic oscillator and the ultrasonic oscillator was turned on. The results of time series observation are shown, and the time-lapse shooting from video shooting is reproduced. FIG. 37A shows a sample placed on an ultrasonic transducer (bright field). FIG. 37B shows a dark state before powering on the ultrasonic transducer (dark field). The light emitted strongly at the moment when the power of the ultrasonic transducer was turned on (Fig. 37C), and this light emission continued thereafter (Fig. 37).
D), when the ultrasonic output is maximized (18V, 0.5
A) The result with the highest emission intensity was obtained.

FIG. 38 shows the results of monitoring the change in the emission intensity of light having a wavelength of 520 nm for 20 seconds before and after the power source of the ultrasonic oscillator was turned on from the off state in the experiment described with reference to FIG. FIG. 38A) and the measurement result (FIG. 38B) of the emission spectrum at the time of the strongest emission intensity. In addition, the stage of the ultrasonic transducer has a problem that heat is generated in a few seconds.
That is, the influence of thermoluminescence was also considered.
Then, SrAl ₂ O ₄ : Eu single crystal flakes were placed on a heat generation stage and observed in a rapid heat generation state, but it was confirmed that no light emission occurred in this state. From these series of experimental facts, it was confirmed and verified for the first time in the world that the substance SrAl ₂ O ₄ : Eu emits light by ultrasonic irradiation. Emission at 520 nm, which is the emission wavelength confirmed during ultraviolet excitation or stress emission, is also observed here.

Although one method has already been described as a method for producing artificial light emitting hair, a method for producing artificial light emitting hair by electrophoresis will be described below as another method. First, the electrophoretic device used will be described. As shown in FIG. 39, an electrophoretic bath 71 contains an electrodeposition coating liquid 73 such as an acrylic melamine system in which SrAl ₂ O ₄ : Eu powder 72 is dispersed,
A base 75 in which the thin metal wires 74 are planted is dipped therein. The thin metal wire 74 is made of, for example, copper or nickel, and has a diameter of 0.01 to 1 mm and a length of about 20 mm, for example. The base 75 is, for example, a silicone resin base, and all the thin metal wires 74 are electrically connected to each other through a conductive layer (not shown) formed on the surface of the silicone resin base. Further, in the electrodeposition coating liquid 73, a metal plate 76 is immersed so as to face a base 75 on which the thin metal wires 74 are planted.

Using the electrophoretic device constructed as described above, artificial luminescent hair is manufactured as follows. That is, as shown in FIG. 39, a DC voltage (for example, 100 to 200 V) is generated between the metal plate 76 and the base 75 on which the thin metal wires 74 are planted, and the base 75 is the positive electrode and the metal plate 76. Is applied so that it becomes a negative electrode. Then, by electrophoresis, the negatively charged SrAl ₂ O ₄ : Eu powder 72 and the electrodeposition coating material are attached so as to cover the periphery of each metal fine wire 74. Around these metal wires 74, these SrAl ₂ O ₄ :
After the Eu powder 72 and the electrodeposition paint have been sufficiently adhered, the base 75 in which the fine metal wires 74 are planted is taken out from the electrodeposition paint liquid 73 and heat-treated at 120 ° C. to cure the resin. In this way, as shown in FIG.
The artificial luminescent hair 79 in which the complex 78 of the SrAl ₂ O ₄ : Eu powder and the resin is formed around the No. ₄ is manufactured. Figure 4
FIG. 1 shows an artificial light emitting hair unit in which artificial light emitting hair 79 is planted on a base 75.

An artificial light-emitting hair 79, in which a composite body 78 of SrAl ₂ O ₄ : Eu powder 72 and a resin is formed to a thickness of 20 μm around the metal fine wire 74 having a diameter of 60 μm thus manufactured
Can be made to emit light by touching or stroking. 41 and 42 show this state, and the reference numeral 80 indicates the fingers of the hand.

Next, another method for producing artificial luminescent hair will be described.
explain about. This method is also based on electrophoresis
is there. However, SrAl₂O_Four: Composite with Eu powder
Glass is used as the material. Specifically, this manufacturing method
In the method, SrAl is used as the electrodeposition coating liquid 73.₂O_Four: Eu
Powder 72 and glass powder (eg PbO-SiO 2₂
-B₂O₃System glass powder) (not shown) dispersed
Isopropanol is used. And with the above manufacturing method
Similarly, a base 75 on which the thin metal wires 74 are planted and a metal plate 76
DC voltage (for example, 100-200V) is applied between
The SrAl around the thin metal wire 74.₂O _Four: Eu powder 7
2 and the electrodeposition paint are sufficiently adhered, and then the metal fine wire 74
Taking out the base 75 in which the
For example, heat treatment is performed at 600 ° C. to cure the glass. this
Thus, as shown in FIG.
On SrAl₂O_Four: Composite 7 of Eu powder 72 and glass
Artificial luminescent hair with 8 formed is produced.

An artificial light-emitting hair 7 in which a composite 78 of SrAl ₂ O ₄ : Eu powder 72 and glass having a thickness of 20 μm was formed around the metal fine wire 74 having a diameter of 60 μm thus manufactured.
9 emits light when touched or stroked.

The embodiments of the present invention have been specifically described above, but the present invention is not limited to the above-described embodiments, and various modifications can be made based on the technical idea of the present invention.

For example, the numerical values, structures, shapes, materials, processes, etc. mentioned in the above embodiments are merely examples, and different numerical values, structures, shapes, materials, processes, etc. may be used as necessary. Good.

[0183]

As described above, according to the present invention, it is possible for a human to lightly touch a fluorescent material or a composite material with his or her hand or finger to bend them greatly with a soft feeling, resulting in stress emission. It becomes possible, or it becomes possible to illuminate a predetermined part by using an electric signal from the outside by utilizing piezoelectric vibration or the like, which can bring about great innovation in various fields such as an entertainment robot.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an X-ray diffraction pattern at each stage of a synthesis process of SrAl ₂ O ₄ : Eu ceramics powder by a solid phase reaction.

FIG. 2 is a schematic diagram showing an X-ray diffraction pattern at each stage of a synthesis process of SrAl ₂ O ₄ : Eu ceramics powder by a solid phase reaction.

FIG. 3 is a schematic diagram showing an X-ray diffraction pattern at each stage of the synthesis process of SrAl ₂ O ₄ : Eu ceramics powder by solid-state reaction.

FIG. 4 is a schematic diagram showing an X-ray diffraction pattern at each stage of the synthesis process of SrAl ₂ O ₄ : Eu ceramic powder by solid-state reaction.

FIG. 5 is a drawing-substituting photograph for explaining a state of light emission from a sheet of a composite material according to the present invention when the sheet is folded.

FIG. 6 is a schematic diagram showing an entertainment robot using a material that emits light when touched as artificial skin.

FIG. 7 is a schematic diagram showing the correlation between the weight ratio of SrAl ₂ O ₄ : Eu powder and the emission intensity in a composite material sheet of SrAl ₂ O ₄ : Eu powder and polyester resin.

FIG. 8: Composite material sheet of SrAl ₂ O ₄ : Eu powder and polyester resin and SrAl ₂ O ₄ : Eu + Dy
It is a drawing substitute photograph which shows the afterglow characteristic of the composite material sheet of powder and resin.

FIG. 9 is a schematic diagram showing an ultraviolet excitation-emission spectrum of SrAl ₂ O ₄ : Eu powder and its afterglow characteristics.

FIG. 10 is a schematic diagram showing an ultraviolet excitation-emission spectrum of SrAl ₂ O ₄ : Eu + Dy powder and its afterglow characteristics.

FIG. 11 is a schematic diagram showing a band image regarding emission of SrAl ₂ O ₄ : Eu.

FIG. 12 is a drawing-substituting photograph showing an observation result of reversible luminescence characteristics by applying / releasing pressure to a composite material sheet according to the present invention.

FIG. 13 is a drawing-substituting photograph showing a state of light emission when a composite material sheet according to the present invention is brought into contact with a horn that is vibrating ultrasonically.

FIG. 14 is a drawing-substituting photograph showing a state of light emission when the composite material sheet according to the present invention is placed on an ultrasonic oscillator and the ultrasonic oscillator is turned on / off.

FIG. 15 is a schematic diagram conceptually showing an artificial skin system using the composite material according to the present invention.

FIG. 16 is a schematic diagram showing an entertainment robot using artificial skin according to the present invention.

FIG. 17 is a schematic diagram and a drawing-substituting photograph showing artificial coloring skin using a sponge-like or network-like stress-stimulated luminescent material.

FIG. 18 is a schematic diagram showing the structure of an inorganic / organic hybrid material according to the present invention.

FIG. 19 is a schematic diagram showing the flexibility of a sheet made of an inorganic / organic hybrid material according to the present invention.

FIG. 20 is a schematic diagram showing a method of manufacturing a light emitting device in which a fluorescent substance and a piezoelectric material are fused.

FIG. 21 is a schematic diagram for explaining a method of manufacturing a light emitting device in which a fluorescent substance and a surface acoustic wave material are fused.

FIG. 22 is a cross-sectional view showing a light emitting device with integrated MOSFET.

23 is a schematic diagram showing a two-dimensional light emitting device by an active matrix using the light emitting device with integrated MOSFET shown in FIG. 22. FIG.

FIG. 24 is a schematic diagram showing a composite material in which a stress-stimulated luminescent material is provided at the grain boundaries of piezoelectric ceramic microcrystals.

25 is a schematic diagram for explaining the operation of the light emitting device using the composite material shown in FIG.

FIG. 26 is a schematic diagram showing a light emitting element in which stress emission dots are formed on an actuator substrate by an inkjet method.

FIG. 27 is a schematic diagram showing an ultrasonic road sign light emitting system.

FIG. 28 is a schematic diagram showing artificial skin according to the present invention.

FIG. 29 is a drawing-substituting photograph showing a state where the composite material sheet according to the present invention is brought into contact with one end of an optical fiber.

FIG. 30 is a drawing-substituting photograph showing a state where the composite material sheet according to the present invention is brought into contact with one end of an optical fiber and an external force is applied to the composite material sheet, and the environment is darkened.

FIG. 31 is a drawing-substituting photograph showing a state where the composite material sheet according to the present invention is brought into contact with one end of an optical fiber and an external force is applied to the composite material sheet to darken the environment.

FIG. 32 is a schematic diagram showing a time change of the intensity of light having a wavelength of 520 nm before and after applying the composite material sheet according to the present invention to one end of an optical fiber and applying an external force to the composite material sheet.

FIG. 33 is a drawing-substitute photograph showing an example of the artificial light-emitting hair according to the present invention.

FIG. 34 is a drawing-substitute photograph showing an example of the artificial light-emitting hair according to the present invention.

FIG. 35 is a drawing-substituting photograph showing a state where artificial light-emitting hair according to the present invention is held by fingers of both hands.

FIG. 36 is a drawing-substituting photograph showing a state of light emission when the artificial light-emitting hair according to the present invention is held by the fingers of both hands and bent.

FIG. 37 is a drawing-substitute photograph showing a state of light emission when an SrAl ₂ O ₄ : Eu single crystal thin piece is placed on an ultrasonic oscillator and the ultrasonic oscillator is turned on / off.

FIG. 38 is a schematic diagram showing a change over time in the emission intensity of light having a wavelength of 520 nm from an SrAl ₂ O ₄ : Eu single crystal thin piece and an emission spectrum.

FIG. 39 is a schematic diagram for explaining a method for manufacturing artificial light-emitting hair according to the present invention.

FIG. 40 is a schematic diagram showing artificial light-emitting hair according to the present invention.

FIG. 41 is a schematic diagram showing an artificial light emitting hair unit according to the present invention.

FIG. 42 is a schematic diagram showing an artificial light emitting hair unit according to the present invention.

[Explanation of symbols]

11, 21 ... Si substrate, 13 ... Lower electrode, 1
4, 23, 38 ... Piezoelectric thin film, 15 ... Upper electrode,
16, 26, 41 ... Stress emission layer, 18 ... Upper transparent electrode layer, 24, 25, 39, 40 ... Comb-shaped electrode, 5
1 ... PZT microcrystal, 52 ... SrAl ₂ O ₄ : E
u, 53 ... Ceramic material, 54, 55 ... Electrode, 61 ... Actuator substrate, 62 ... Stress emission dots, 63 ... Actuator material, 72 ...
SrAl ₂ O ₄ : Eu powder, 73 ... Electrodeposition coating liquid, 7
4 ... Metal fine wire, 75 ... Base, 76 ... Metal plate, 79 ... Artificial light-emitting hair

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 5C094 C09D 7/12 C09D 7/12 11/00 11/00 201/00 201 / 00 C09K 11/00 C09K 11/00 AF 11/08 11/08 B Z G09F 9/30 360 G09F 9/30 360 (72) Inventor Naomi Nagasawa 6-735 Kita-Shinagawa, Shinagawa-ku, Tokyo -In-house F-term (reference) 4G076 AA02 AB18 BA17 CA33 DA30 4H001 CA04 CF02 XA08 XA13 XA14 XA30 XA31 XA38 YA00 YA22 YA25 YA63 4J002 BB021 BB111 BC021 BF011 18601 BG01 HA186206 CG001 DE086206 DE03CK0 HA436 KA08 KA12 KA14 KA18 KA19 KA21 KA22 4J039 BA06 BA13 BA30 BA31 BA32 BA35 BA39 BE01 EA28 5C094 AA43 AA56 BA02 BA21 CA18 CA19 DA09 DA13 FB01 FB02 FB20 GA10 JA08 (54) [Title of Invention] Fluorescent substance, composite material, coating material, paint, ink, artificial skin, artificial skin contact information processing method, artificial luminescent skin, artificial luminescent hair, luminescent element, electronic device, luminescence System, display system, flexible light emitting material, ultrasonic light emitting substance, traffic sign, light emitting method, composite material manufacturing method and light emitting element manufacturing method

Claims (148)

[Claims] 1. A fluorescent substance which emits light depending on the rate of change of stress with time. 2. A fluorescent substance characterized in that the emission intensity changes depending on the rate of change of stress with time. 3. A fluorescent substance which emits light depending on the rate of application or release of external force. 4. A fluorescent substance, wherein the emission intensity changes depending on the rate of application or release of external force. 5. A composite material, which emits light depending on the rate of change of stress with time. 6. A composite material in which the emission intensity changes depending on the rate of change of stress over time. 7. A composite material which emits light depending on the rate of application or release of an external force. 8. A composite material in which the emission intensity changes depending on the rate of application or release of an external force. 9. A composite material comprising a fluorescent substance and another substance, which emits light depending on the rate of change of stress with time. 10. A composite material comprising a fluorescent substance and another substance, wherein the emission intensity changes depending on the time change rate of stress. 11. A composite material comprising a fluorescent substance and another substance, which emits light depending on the rate of application or release of an external force. 12. A composite material comprising a fluorescent substance and another substance, wherein the emission intensity changes depending on the rate of application or release of external force. 13. A fluorescent substance which emits light only by touching it with a hand. 14. A composite material, which emits light only by touching with a hand. 15. A fluorescent substance and another substance, A composite material that emits light when simply touched. 16. A fluorescent substance which emits light by causing elastic vibration. 17. A composite material which emits light by causing elastic vibration. 18. A composite material comprising a fluorescent substance and another substance, which emits light when elastic vibration is caused. 19. A fluorescent substance which emits light when a sound wave is applied. 20. A composite material which emits light by applying a sound wave. 21. A composite material comprising a fluorescent substance and another substance, which emits light when a sound wave is applied. 22. A fluorescent substance which emits light when exposed to ultrasonic waves. 23. A composite material which emits light when exposed to ultrasonic waves. 24. A composite material comprising a fluorescent substance and another substance, which emits light when exposed to ultrasonic waves. 25. The other material is an elastic body, and the other material is an elastic body.
The composite material according to 1 or 24. 26. The composite material according to claim 25, wherein the weight ratio of the fluorescent substance is 30% or more and less than 100%. 27. The composite material according to claim 25, wherein the elastic body is an organic material. 28. The composite material according to claim 25, wherein the Young's modulus of the elastic body is 10 MPa or more. 29. The elastic body is polymethylmethacrylate, ABS resin, polycarbonate, polystyrene,
It is characterized by being composed of at least one material selected from the group consisting of polyethylene, polypropylene, polyacetal, urethane resin, polyester, epoxy resin, silicone rubber, an organic silicon compound having a siloxane bond, and an organic piezoelectric material. Claim 25
The described composite material. 30. The composite material according to claim 25, wherein the elastic body is an inorganic glass. 31. The fluorescent material is an oxide containing aluminum, gallium or zinc as one of the constituent elements, and the fluorescent material is characterized in that:
The fluorescent substance according to 19 or 22. 32. The fluorescent material is an oxide containing aluminum, gallium or zinc as one of its constituent elements.
The composite material according to 18, 21 or 24. 33. The fluorescent substance is a substance in which an oxide of an alkaline earth metal and aluminum is used as a base material and which is doped with a rare earth element. The fluorescent substance according to 13, 16, 19 or 22. 34. The fluorescent substance comprises an oxide of an alkaline earth metal and aluminum as a base material, and is doped with a rare earth element. The composite material according to 15, 18, 21 or 24. 35. The fluorescent substance according to claim 33, wherein only one kind of the rare earth element is doped. 36. The composite material according to claim 34, wherein only one kind of the rare earth element is doped. 37. The fluorescent substance as claimed in claim 1, wherein the fluorescent substance is doped with manganese and / or titanium. 38. The composite material according to claim 9, 10, 11, 11, 12, 15, 18, 21 or 24, wherein said fluorescent material is doped with manganese and / or titanium. 39. The fluorescent substance is SrAl ₂ O ₄ : E.
u is the value of claim 1, 2, 3, 4, 1
The fluorescent substance according to 3, 16, 19 or 22. 40. The fluorescent substance is SrAl ₂ O ₄ : E.
26. The elastic body is u, and the elastic body is polyester, acrylic resin, or a mixture thereof.
Or the composite material according to 26. 41. A sheet-like shape having a thickness of 1 mm or less, 1, 2, 3, 4, 13,
The fluorescent substance according to 16, 19, or 22. 42. The sheet-like shape having a thickness of 1 mm or less.
The composite material according to 15, 18, 21 or 24. 43. A fibrous or fibrous shape having a thickness of 1 mm or less.
The fluorescent substance according to 2, 3, 4, 13, 16, 19 or 22. 44. The fiber or fiber-like shape having a thickness of 1 mm or less.
The composite material according to 0, 11, 12, 15, 18, 21 or 24. 45. The fluorescent substance according to claim 1, wherein the fluorescent substance has a fiber-like, sponge-like or network-like shape. 46. The fluorescent material has a fiber-like, sponge-like or network-like shape.
Or the composite material according to 24. 47. The fluorescent substance according to claim 45, wherein the constituent element of the fluorescent substance contains aluminum, gallium or zinc. 48. The composite material according to claim 46, wherein the constituent element of the fluorescent substance contains aluminum, gallium or zinc. 49. The fluorescent substance according to claim 45, wherein the constituent elements of the fluorescent substance include aluminum and silicon. 50. The composite material according to claim 46, wherein the constituent elements of the fluorescent substance include aluminum and silicon. 51. The fluorescent substance has a diameter of 100 nm.
Claims 1 and 2, characterized by comprising the following fine particles:
The fluorescent substance according to 3, 4, 13, 16, 19 or 22. 52. The fluorescent material has a diameter of 100 nm.
26. The composite material according to claim 25, comprising the following fine particles. 53. The fluorescent substance according to claim 51, wherein the fluorescent substance is crystalline. 54. The composite material according to claim 52, wherein the fluorescent substance is crystalline and the elastic body is amorphous. 55. The composite material according to claim 52, which is gel-like as a whole. 56. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and emits light depending on a time change rate of stress, comprising a polysiloxane compound and a metal alkoxide. dehydration·
A method for producing a composite material, which comprises using a condensation reaction. 57. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and whose emission intensity changes depending on the rate of change of stress over time, comprising a polysiloxane compound and Dehydration of metal alkoxide
A method for producing a composite material, which comprises using a condensation reaction. 58. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body and emits light depending on the rate of application or release of an external force, comprising a polysiloxane compound and a metal. Dehydration of alkoxide
A method for producing a composite material, which comprises using a condensation reaction. 59. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and whose emission intensity changes depending on the rate of application or release of an external force, comprising polysiloxane. Dehydration of compounds and metal alkoxides
A method for producing a composite material, which comprises using a condensation reaction. 60. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body and emits light only by touching with a hand, comprising: dehydration of a polysiloxane compound and a metal alkoxide;
A method for producing a composite material, which comprises using a condensation reaction. 61. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and emits light when elastic vibration is generated, comprising: dehydration of a polysiloxane compound and a metal alkoxide;
A method for producing a composite material, which comprises using a condensation reaction. 62. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and emits light by applying a sound wave, comprising dehydration of a polysiloxane compound and a metal alkoxide.
A method for producing a composite material, which comprises using a condensation reaction. 63. A method for producing a composite material, which comprises a fluorescent substance composed of fine particles having a diameter of 100 nm or less and an elastic body, and emits light when exposed to ultrasonic waves, the method comprising dehydrating a polysiloxane compound and a metal alkoxide.
A method for producing a composite material, which comprises using a condensation reaction. 64. The composite material according to claim 9, wherein the other substance is an organic conductive substance which takes in ions and is deformed. 65. The composite material according to claim 64, wherein the organic conductive substance is a heteroaromatic ring-type conductive polymer. 66. The method according to claim 9, wherein the other substance is a polymer gel material.
The composite material according to 18, 21 or 24. 67. The polymer gel material is a water-soluble non-electrolyte polymer gel having a heat displacement function, an electrolyte polymer gel that is displaced by pH, or a combination of a polymer compound that is electrically displaced and a surfactant. 67. The composite material according to claim 66, which is at least one material selected from the group consisting of a polyvinyl alcohol material and a polypyrrole material. 68. The water-soluble non-electrolyte polymer gel having a heat displacement function is polyvinyl methyl ether or poly-N-isopropylacrylamide, and the electrolyte polymer gel which is displaced by the pH is polyacrylonitrile, and 68. The composite material according to claim 67, wherein the polymer compound causing displacement is polyacrylamido-2-methylpropanesulfonic acid. 69. A coating material containing a fluorescent substance that emits light depending on the rate of change of stress with time. 70. A coating material containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress over time. 71. A coating material containing a fluorescent substance that emits light depending on the rate of change of stress with time. 72. A coating material containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time. 73. An ink containing a fluorescent substance which emits light depending on the rate of change of stress with time. 74. An ink containing a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time. 75. An artificial skin containing a fluorescent substance which emits light depending on the rate of change of stress with time. 76. An artificial skin containing a fluorescent substance whose luminescence intensity changes depending on the rate of change of stress over time. 77. A skin layer made of an artificial skin material, a plurality of optical fibers penetrating the skin layer in a predetermined arrangement, and provided on one end of the optical fiber on one surface side of the skin layer. And a fluorescent substance that emits light depending on the rate of change of stress over time, or a composite material that consists of a fluorescent substance and another substance and emits light depending on the rate of change over time of stress. Artificial skin. 78. The artificial skin according to claim 77, wherein the plurality of optical fibers are provided in a two-dimensional array. 79. A skin layer made of an artificial skin material, a plurality of optical fibers penetrating the skin layer in a predetermined arrangement, and provided on one end of the optical fiber on one surface side of the skin layer. , Contact information of artificial skin having a fluorescent substance that emits light depending on the time change rate of stress, or a composite material consisting of a fluorescent substance and another substance that emits light depending on the time change rate of stress A treatment method, wherein the position of an optical fiber from which the light is emitted from the other end of the plurality of optical fibers and / or the emitted light when another object comes into contact with the one surface of the artificial skin The contact information processing method for artificial skin, wherein the contact information of the object is obtained from the strength of the object. 80. The contact information processing method for artificial skin according to claim 79, wherein the plurality of optical fibers are provided in a two-dimensional array. 81. A fluorescent material or a composite material comprising a fluorescent material and another material, which has a fibrous shape or a fibrous shape with a thickness of 1 mm or less and emits light depending on the rate of change of stress with time. Artificial luminescent skin, characterized by being implanted in artificial skin. 82. A fluorescent material or a composite material composed of a fluorescent material and another material, which has a fibrous shape or a fibrous shape with a thickness of 1 mm or less and emits light depending on the rate of change of stress with time. Artificial luminescent hair characterized by being used. 83. A fluorescent substance or a composite material comprising a fluorescent substance and another substance, which has a fibrous or fibrous shape with a thickness of 1 mm or less and emits light depending on the rate of change of stress with time. A method for producing artificial luminescent hair using, wherein one end of a tube is inserted into a liquid containing fine particles of the fluorescent substance or a liquid containing fine particles of the fluorescent substance and the other substance in a liquid state, A method for producing artificial luminescent hair, characterized in that suction is applied from the other end to fill the liquid in the tube, and then the liquid filled in the tube is solidified. 84. A fluorescent substance or a composite material comprising a fluorescent substance and another substance, which has a fibrous or fibrous shape with a thickness of 1 mm or less and emits light depending on the rate of change of stress with time. A method for producing artificial luminescent hair using, wherein an electrocoating liquid containing fine particles of the fluorescent substance or an electrocoating liquid containing fine particles of the fluorescent substance and a raw material of the other substance is electrically conductive. Of the artificial light-emitting hair characterized in that the fluorescent substance fine particles or the fluorescent substance fine particles and the other substance are adhered to the surface of the core wire by an electrophoretic method. Production method. 85. A light emitting device using a fluorescent substance that emits light depending on the rate of change of stress with time. 86. A light emitting device using a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time. 87. A light emitting device comprising: a piezoelectric vibrator; and a fluorescent substance, which is joined to the piezoelectric vibrator and emits light depending on the piezoelectric vibration. 88. A light emitting device comprising: a piezoelectric vibrator; and a composite material, which is joined to the piezoelectric vibrator, is made of a fluorescent substance and another substance, and emits light depending on piezoelectric vibration. 89. A piezoelectric vibrator, and a composite material, which is joined to the piezoelectric vibrator, is made of a fluorescent substance and another substance, and changes in emission intensity depending on the amplitude and / or frequency of the piezoelectric vibration. A light-emitting element having. 90. A light emitting device comprising: a surface acoustic wave device; and a fluorescent substance, which is joined to the surface acoustic wave device and emits light depending on the amplitude and / or frequency of elastic vibration. 91. A surface acoustic wave device, and a composite material, which is joined to the surface acoustic wave device, is made of a fluorescent substance and another substance, and emits light depending on the amplitude and / or frequency of elastic vibration. A light emitting element characterized by the above. 92. A composite material comprising a surface acoustic wave element and a fluorescent substance and another substance bonded to the surface acoustic wave element, the emission intensity of which changes depending on the amplitude and / or frequency of elastic vibration. A light-emitting device having: 93. A light emitting device having a structure in which a thin film made of a piezoelectric material and a thin film made of a fluorescent substance that emits light depending on piezoelectric vibration are stacked. 94. A light emitting device having a structure in which a thin film made of a piezoelectric material and a thin film made of a composite material made of a fluorescent substance and another substance and emitting light depending on piezoelectric vibration are laminated. element. 95. A structure in which a thin film made of a piezoelectric material and a thin film made of a composite material which is made of a fluorescent substance and another substance and whose emission intensity changes depending on piezoelectric vibration are laminated. Light emitting element. 96. The light emitting device according to claim 93, wherein the thin film made of the piezoelectric material and the thin film made of the fluorescent substance are epitaxially lattice-matched and laminated. 97. The light emitting device according to claim 94, comprising a pair of electrodes facing each other with the thin film made of the piezoelectric material interposed therebetween. 98. The light emitting device according to claim 95, comprising a pair of electrodes facing each other with the thin film made of the piezoelectric material interposed therebetween. 99. The light emitting device according to claim 94, wherein a pair of comb-shaped electrodes facing each other are provided on one surface of the thin film made of the piezoelectric material. 100. The light emitting device according to claim 95, wherein a pair of comb-shaped electrodes facing each other are provided on one surface of the thin film made of the piezoelectric material. 101. The light emission according to claim 99, further comprising a MIS transistor for controlling light emission, wherein the drain of the MIS transistor and one of the pair of comb-shaped electrodes are electrically connected. element. 102. The light emission according to claim 100, further comprising a MIS transistor for light emission control, wherein a drain of the MIS transistor and one of the pair of comb-shaped electrodes are electrically connected. element. 103. The thin film made of the piezoelectric material is Si.
The light emitting device according to claim 94, which is epitaxially lattice-matched with the CeO ₂ thin film formed on the substrate. 104. The thin film made of the piezoelectric material is Si
The light emitting device according to claim 95, which is epitaxially lattice-matched with the CeO ₂ thin film formed on the substrate. 105. The light emitting device according to claim 88, 89, 91, 92, 94 or 95, wherein the other substance is an elastic body. 106. The light emitting device according to claim 101, wherein the light emitting device is one unit of an active matrix device. 107. The light emitting device according to claim 102, wherein the light emitting device is one unit of an active matrix device. 108. The other material is a piezoelectric material, claim 9, 10, 11, 12, 15, 1
The composite material according to 8, 21, or 24. 109. The composite material according to claim 108, comprising a particle portion and a grain boundary portion, said particle portion mainly consisting of said piezoelectric material, and said grain boundary portion mainly consisting of said fluorescent substance. . 110. A light emitting device using a composite material mainly composed of a fluorescent substance and a piezoelectric material, which emits light depending on a time change rate of stress, wherein the composite material is composed of a grain portion and a grain boundary portion. The grain portion is mainly composed of the piezoelectric material, the grain boundary portion is mainly composed of the fluorescent material, and an electrostriction is induced in the composite material by the input of an electric signal from the outside. A light emitting device, characterized in that an electrode is provided so that light emission can be obtained from the fluorescent substance in the boundary portion. 111. A light emitting device using a composite material mainly composed of a fluorescent substance and a piezoelectric material, wherein the emission intensity changes depending on the rate of change of stress with time, wherein the composite material comprises a particle portion and a grain boundary. Part, the particle part is mainly composed of the piezoelectric material, the grain boundary part is mainly composed of the fluorescent substance, and an electrostriction is induced in the composite material by the input of an electric signal from the outside. As a light emitting element, an electrode is provided so that light can be obtained from the fluorescent substance in the grain boundary portion. 112. The composite material according to claim 108, wherein the piezoelectric material has an ABO ₃ type perovskite-related crystal structure. 113. The light emitting device according to claim 110, wherein the piezoelectric material has an ABO ₃ type perovskite-related crystal structure. 114. The piezoelectric material is a PbTiO ₃ based material, a PbZrO ₃ based material, a Pb (ZrTi) O ₃ based material, a Pb (ZnNb) O ₃ based material or a Pb (MgN) material.
The composite material according to claim 108 or 109, which is b) at least one material selected from the group consisting of O ₃ -based materials or a solid solution material thereof. 115. The piezoelectric material is a PbTiO ₃ based material, a PbZrO ₃ based material, a Pb (ZrTi) O ₃ based material, a Pb (ZnNb) O ₃ based material or a Pb (MgN) material.
The light emitting device according to claim 110 or 111, which is b) at least one material selected from the group consisting of O ₃ -based materials or a solid solution material thereof. 116. The piezoelectric material is Pb (ZrTi) O.
_{It is a 3} type material, and the fluorescent substance is SrAl ₂ O ₄ : E.
The composite material according to claim 108 or 109, characterized in that it is u. 117. The piezoelectric material is Pb (ZrTi) O.
_{It is a 3} type material, and the fluorescent substance is SrAl ₂ O ₄ : E.
The light emitting device according to claim 110 or 111, which is u. 118. The composite material according to claim 108, wherein the fluorescent substance is an aluminate-based glass phase containing a rare earth element. 119. The light emitting device according to claim 110 or 111, wherein the fluorescent material is an aluminate glass phase containing a rare earth element. 120. The fluorescent material is SrAl ₂ O ₄ :
The composite material according to claim 108 or 109, which is a glass phase containing Eu fine particles. 121. The fluorescent material is SrAl ₂ O ₄ :
The light emitting device according to claim 110 or 111, which is a glass phase containing Eu particles. 122. A method for producing a composite material which mainly comprises a fluorescent substance and a piezoelectric material and emits light depending on the rate of change of stress with time, wherein the mixture contains at least Sr, Al and Eu and a glass forming substance. And a powder obtained by crushing the glass phase and the piezoelectric material are mixed and heat-treated to form SrAl from the glass phase. ₂ O ₄ : A method for producing a composite material, comprising a step of depositing Eu fine particles. 123. A method for producing a composite material, which is mainly composed of a fluorescent substance and a piezoelectric material and whose emission intensity changes depending on the rate of change of stress with time, comprising Sr, Al and Eu and a glass-forming substance. A step of melting a mixture containing at least the material and rapidly cooling it from this molten state to generate a glass phase; mixing the powder obtained by crushing the glass phase with the piezoelectric material; A method for producing a composite material, comprising a step of precipitating SrAl ₂ O ₄ : Eu fine particles from a phase. 124. A substrate having an actuator function, and a dot-shaped substance provided on the substrate in a predetermined arrangement and containing a fluorescent substance that emits light depending on a time change rate of stress. Light emitting element. 125. A substrate having an actuator function, and a dot-shaped substance, which is provided in a predetermined arrangement on the substrate and includes a fluorescent substance whose emission intensity changes depending on a time change rate of stress, A light emitting element characterized by. 126. A method of manufacturing a light emitting device, comprising: a substrate having an actuator function; and a dot-shaped substance provided on the substrate in a predetermined arrangement and containing a fluorescent substance that emits light depending on a time change rate of stress. A method for manufacturing a light emitting device, characterized in that the dot-shaped substance is formed by printing on the substrate using the ink containing the fluorescent substance. 127. Light emission comprising a substrate having an actuator function, and a dot-shaped substance provided on the substrate in a predetermined arrangement and containing a fluorescent substance whose emission intensity changes depending on the time change rate of stress. A method for manufacturing a light-emitting element, which is characterized in that the dot-shaped substance is formed by printing on the substrate using the ink containing the fluorescent substance. 128. The method for manufacturing a light-emitting element according to claim 126 or 127, wherein the printing is performed by a printer. 129. The light emitting device according to claim 124, wherein the dot-shaped substance is provided periodically. 130. The method of manufacturing a light emitting device according to claim 126, wherein the dot-shaped substance is provided periodically. 131. The light emitting device according to claim 124 or 125, wherein an element having an actuator function is periodically embedded in the surface of the substrate. 132. The method according to claim 126 or 127, wherein elements having an actuator function are periodically embedded in the surface of the substrate. 133. The structure according to claim 124, wherein the substrate has a polymer actuator function.
The light emitting device described. 134. The structure according to claim 126 or 127, wherein the substrate has a polymer actuator function.
A method for manufacturing a light-emitting device as described above. 135. The polymer actuator comprises a water-soluble non-electrolyte polymer gel having a thermal displacement function, an electrolyte polymer gel that is displaced by pH, a combination of a polymer compound that is electrically displaced and a surfactant, The light emitting device according to claim 133, wherein at least one material selected from the group consisting of a polyvinyl alcohol material and a polypyrrole material is used. 136. The polymer actuator comprises a water-soluble non-electrolyte polymer gel having a heat displacement function, an electrolyte polymer gel that is displaced by pH, a combination of a polymer compound that is electrically displaced and a surfactant, The method for manufacturing a light-emitting element according to claim 134, wherein at least one material selected from the group consisting of polyvinyl alcohol-based materials and polypyrrole-based materials is used. 137. A material containing at least a fluorescent substance that emits light depending on the rate of change in stress over time is formed into a film, droplets, dots, rods, stripes, or bulk ceramics in the two-dimensional plane of the substrate. A flexible light-emitting material, characterized in that a plurality of objects provided in the shape of a circle are connected by a flexible connecting means. 138. A material containing at least a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time is formed into a film shape, a droplet shape, a dot shape, a rod shape, or a stripe shape in the two-dimensional plane of the substrate. Alternatively, the flexible light emitting material is characterized in that a plurality of materials provided in the shape of bulk ceramics are connected by a flexible connecting means. 139. A crystalline material in which only one kind of rare earth element is doped in a matrix of an oxide of an alkaline earth metal and aluminum is obtained by subjecting the crystalline material to a reduction treatment at a temperature of 500 ° C. or higher. Ultrasonic emitting substance. 140. Ultrasonic luminescence obtained by subjecting a crystalline material, in which only one kind of rare earth element is doped in a matrix of an oxide of an alkaline earth metal and aluminum, to a reduction treatment at a temperature of 500 ° C. or higher. A traffic sign that uses a material containing at least a substance and emits light when exposed to ultrasonic waves. 141. An electronic device having a light emitting display unit, wherein the light emitting display unit uses a fluorescent substance that emits light depending on a time change rate of stress. 142. An electronic device having a light-emitting display unit, wherein the light-emitting display unit uses a fluorescent substance whose emission intensity changes depending on a time change rate of stress. 143. A light emitting system comprising: a display section using a fluorescent substance that emits light depending on a rate of change of stress with time; and an ultrasonic wave source for irradiating the display section with ultrasonic waves. . 144. A display unit using a fluorescent substance whose emission intensity changes depending on the rate of change of stress over time, and an ultrasonic source for irradiating the display unit with ultrasonic waves. Luminous system. 145. A display system, comprising: a display section using a fluorescent substance that emits light depending on a rate of change of stress with time; and an ultrasonic wave source for irradiating the display section with ultrasonic waves. . 146. A display unit using a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time, and an ultrasonic source for irradiating the display unit with ultrasonic waves. Display system. 147. A light emitting method, wherein a fluorescent substance that emits light depending on a rate of change of stress with time is used, and light emission is controlled by the rate of change of stress of the fluorescent substance with time. 148. Luminescence characterized by using a fluorescent substance whose emission intensity changes depending on the rate of change of stress with time, and controlling the emission intensity by the rate of change of stress of the fluorescent substance with time Method.