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Thermochromic opaque composition, laminate member employing the same, and three-dimensional member employing said laminate member and capable of concealing and revealing the interior

Assignee: Pilot Ink Co Ltd
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Filing: 1993-10-21
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Granted: 1996-02-13
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Expires: 2013-10-21
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Abstract

Abstract There are provided a thermochromic opaque composition capable of exhibiting change in transparency together with change in color in response to temperature variation, a laminate member employing the same, and a three-dimensional article capable of concealing and revealing the interior, utilizing the laminate member. The thermochromic oaque composition is formed by dispersing a thermochromic material, capable of developing and erasing color by an electron donating-accepting reaction, in small particles in vinyl chloride-vinyl acetate matrix resin. The above-mentioned structure realizes reversible change in transparency, together with change in color, in response to temperature variation, with hysteresis with a temperature difference of 10° C. at minimum to 50° C. between the high and low trigger temperatures.

Inventors

  • 👤 Tsutomu Kito
  • 👤 Kuniyuki Senga
  • 👤 Hiroyuki Hayashi

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 10:15
CPC Classifications
B; B41; B41M; B41M5/00; B41M5/26; B41M5/30; B41M5/305; B41M5/333; B41M5/3333; B41M5/3335; B41M5/337; B41M5/3372; B41M5/3375; B44; B44F; B44F1/00; B44F1/08; C; C09; C09K; C09K9/00; C09K9/02; B41M2205/00; B41M2205/04; B41M5/323; B41M5/327; B41M5/3275; Y; Y10; Y10S; Y10S252/00; Y10S252/962

Claims Analysis

Total Claims: 13
Claim 1
Independent Claim 231 words
A thermochromic opaque composition comprising a dispersion in a vinyl chloride-vinyl acetate copolymer matrix resin of a reversible thermochromic material which is a homogeneous fused composition comprising, with respect to 6 parts by weight of the vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of an electron-donating color-developing organic compound, (b) 0.1 to 3.0 parts by weight a compound having a phenolic hydroxyl radical and (c) 0.5 to 5.0 parts by weight of a compound selected from the group consisting of alcohols, esters, ketones and carboxylic acids, wherein said vinyl chloride-vinyl acetate copolymer resin has an average molecular weight within a range from 7,000 to 50.000 and has constituent monomer ratios of vinyl chloride: vinyl acetate within a range of 60 to 92: 8 to 40%, and wherein said reversible thermochromic material is dispersed in particles of a size within a range of 0.1 to 2.0 μm, and said thermochromic opaque composition being capable of exhibiting reversible change in transparency together with change in color in response to temperature variation to exhibit a transparent state in a temperature range above a high trigger temperature and a colored opaque state in a temperature range below a low trigger temperature, with a hysteresis having a temperature difference of 10° C. to 50° C., both states being selectively held in a temperature range between said low and high trigger temperatures.
Claim 2
Dependent Claim 231 words
A thermochromic opaque composition comprising a dispersion in a vinyl chloride-vinyl acetate copolymer matrix resin of a reversible thermochromic material which is a homogeneous fused composition comprising, with respect to 6 parts by weight of the vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of an electron-donating color-developing organic compound, (b) 0.1 to 3.0 parts by weight a compound having a phenolic hydroxyl radical and (c) 0.5 to 5.0 parts by weight of a compound selected from the group consisting of alcohols, esters, ketones and carboxylic acids, wherein said vinyl chloride-vinyl acetate copolymer resin has an average molecular weight within a range from 7,000 to 50.000 and has constituent monomer ratios of vinyl chloride: vinyl acetate within a range of 60 to 92: 8 to 40%, and wherein said reversible thermochromic material is dispersed in particles of a size within a range of 0.1 to 2.0 μm, and said thermochromic opaque composition being capable of exhibiting reversible change in transparency together with change in color in response to temperature variation to exhibit a transparent state in a temperature range above a high trigger temperature and a colored opaque state in a temperature range below a low trigger temperature, with a hysteresis having a temperature difference of 10° C. to 50° C., both states being selectively held in a temperature range between said low and high trigger temperatures.
Claim 3
Dependent Claim 33 words
A thermochromic opaque composition according to claim 1, further comprising, with respect to 100 parts by weight of said composition, a dispersing agent in a ratio of 0.002 to 0.5 parts by weight.
Claim 4
Dependent Claim 79 words
A thermochromic opaque composition according to claim 1, wherein at least 50 wt. % of the compound having phenolic hydroxyl radical is selected from the compound represented by the following general formula: ##STR2## wherein R1 stands for H or CH 3 , R2 stands for C n H 2n+1 (4<n<11), which is a straight-chain or branched chain alkyl radical, or R1=R2=CF 3 , and X stands for a substituent which is H or CH 3 on the aromatic ring.
Claim 5
Dependent Claim 123 words
A thermochromic opaque composition according to claim 1, wherein said component (c) is one or more esters selected from (a) esters each consisting of a monobasic fatty acid and an aliphatic or alicyclic monohydric alcohol and having 10 or more carbon atoms in total, (b) polybasic acid esters each consisting of an aliphatic di- or polybasic carboxylic acid and an aliphatic or alicyclic monohydric alcohol and having 28 or more carbon atoms in total, (c) esters each consisting of an aliphatic di- or polyhydric alcohol and a monobasic fatty acid and having 26 or more carbon atoms in total, and (d) esters each consisting of an aromatic dihydric alcohol and a monobasic fatty acid and having 28 or more carbon atoms in total.
Claim 6
Dependent Claim 243 words
A laminate member comprising, a substrate and a laminated layer of a thermochromic opaque composition comprising a dispersion in a vinyl chloride-vinyl acetate copolymer matrix resin of a reversible thermochromic material which is a homogeneous fused composition comprising with respect to 6 parts by weight of the vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of an electron-donating color-developing organic compound, (b) 0.1 to 3.0 parts by weight of a compound having a phenolic hydroxyl radical and (c) 0.5 to 5.0 parts by weight of a compound selected from the group consisting of alcohols, esters, ketones and carboxylic acids, wherein said vinyl chloride-vinyl acetate copolymer resin has an average molecular weight within a range from 7,000 to 50,000 and has constituent monomer ratios of vinyl chloride: vinyl acetate within a range of 60 to 92: 8 to 40% and wherein said reversible thermochromic material is dispersed in particles of a size within a range of 0.1 to 2.0 μm, and said thermochromic opaque composition being capable of exhibiting reversible change in transparency together with change in color in response to temperature variation to exhibit a transparent state in a temperature range above a high trigger temperature and a colored opaque state in a temperature range below a low trigger temperature, with a hysteresis having a temperature difference of 10° C. to 50° C., both states being selectively held in a temperature range between said low and high trigger temperatures.
Claim 7
Dependent Claim 243 words
A laminate member comprising, a substrate and a laminated layer of a thermochromic opaque composition comprising a dispersion in a vinyl chloride-vinyl acetate copolymer matrix resin of a reversible thermochromic material which is a homogeneous fused composition comprising with respect to 6 parts by weight of the vinyl chloride-vinyl acetate copolymer resin, (a) 0.05 to 2.0 parts by weight of an electron-donating color-developing organic compound, (b) 0.1 to 3.0 parts by weight of a compound having a phenolic hydroxyl radical and (c) 0.5 to 5.0 parts by weight of a compound selected from the group consisting of alcohols, esters, ketones and carboxylic acids, wherein said vinyl chloride-vinyl acetate copolymer resin has an average molecular weight within a range from 7,000 to 50,000 and has constituent monomer ratios of vinyl chloride: vinyl acetate within a range of 60 to 92: 8 to 40% and wherein said reversible thermochromic material is dispersed in particles of a size within a range of 0.1 to 2.0 μm, and said thermochromic opaque composition being capable of exhibiting reversible change in transparency together with change in color in response to temperature variation to exhibit a transparent state in a temperature range above a high trigger temperature and a colored opaque state in a temperature range below a low trigger temperature, with a hysteresis having a temperature difference of 10° C. to 50° C., both states being selectively held in a temperature range between said low and high trigger temperatures.
Claim 8
Dependent Claim 14 words
A laminate member according to claim 5, wherein said substrate is a transparent substrate.
Claim 9
Dependent Claim 36 words
A laminate member according to claim 5, wherein said substrate exhibits at least one optical property selected from the group consisting of lustre, lustrous reflectance, optical interference, iridescence, holographic property, metallic lustre, pearl lustre and fluorescence.
Claim 10
Dependent Claim 32 words
A laminate member according to claim 5, wherein said substrate is provided thereon with an undercoat layer consisting of methacrylic resin with the glass transition point at least equal to 90° C.
Claim 11
Dependent Claim 38 words
A laminate member according to claim 5, wherein the layer of the thermochromic opaque composition is provided thereon with a layer consisting of transparent methacrylic or acrylic resin or copolymer resin thereof, soluble in alcohol or aliphatic hydrocarbon.
Claim 12
Dependent Claim 46 words
A three-dimensional article capable of concealing or revealing the interior, of which at least a part is composed of the laminate member according to claim 5, 6, 8 or 9, whereby an object inside said article can be concealed or revealed in response to temperature variation.
Claim 13
Dependent Claim 18 words
A three-dimensional article according to claim 10, which is a toy, a stationary article or a teaching aid.

References Cited (Backward Citations)

US4028118A Cited
JPS57123283A Cited
US4421560A Cited
US4601588A Cited
US4732810A Cited
JPS62101684A Cited
US4826550A Cited
EP0523888A1 Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1999-02-12 1999-08-14 2000-02-13 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 2003-02-12 2003-08-14 2004-02-13 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2007-02-12 2007-08-14 2008-02-13 $7700.00 Window Closed / Lapsed

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